Thermally stable polymers, method of preparation, and articles made therefrom

ABSTRACT

The present invention provides compositions comprising (a) a thermally stable polymer comprising resorcinol arylate polyester chain members substantially free of anhydride linkages linking at least two mers of the polymer chain, and (b) at least one auxiliary stabilizer additive selected from the group consisting of 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane. Both multilayer and unitary articles comprising the composition are also provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.09/908,396, filed Jul. 18, 2001 now U.S. Pat. No. 6,610,409, which is acontinuation-in-part of U.S. application Ser. No. 09/368,706, filed Aug.5, 1999, now U.S. Pat. No. 6,306,507, which claims the benefit of U.S.Provisional Application No. 60/134,692, filed May 18, 1999, and whichapplications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to thermally stable, polymers comprisingpolyester chain members derived from at least one 1,3-dihydroxybenzenemoiety and at least one aromatic dicarboxylic acid moiety (oftenreferred to hereinafter as resorcinol arylate chain members), a methodfor their preparation, and multilayer articles made therefrom.

Various polymeric articles have a problem of long term colorinstability. In many cases this instability is seen as yellowing of thepolymer, detracting from its attractiveness and also transparency whenthe polymer was initially transparent. Loss of gloss can also be anundesirable long term phenomenon.

Yellowing of polymers is often caused by the action of ultravioletradiation, and such yellowing is frequently designated “photoyellowing”.Numerous means for suppressing photoyellowing have been employed andproposed. Many of these involve incorporation in the polymer ofultraviolet absorbing compounds (UVA's). For the most part, UVA's arelow molecular weight compounds, which must be employed at relatively lowlevels, typically up to 1% by weight, to avoid degradation of thephysical properties of the polymer such as impact strength and hightemperature properties as reflected in heat distortion temperature.Another problem of concern with polymers such as aromatic polycarbonatesand addition polymers of alkenylaromatic compounds such as styrene issusceptibility to attack by organic liquids.

One way of protecting a resinous article against photoyellowing and lossof gloss is to apply a coating of a weatherable second polymer, the term“weatherable” as used herein signifying resistance to such phenomena.Coatings made from polyesters containing resorcinol arylate units oftenpossess good weatherability properties. The arylate moieties typicallycontain isophthalate, terephthalate, and especially mixtures of iso- andterephthalate units. Polyesters of resorcinol with mixtures ofisophthalate and terephthalate chain members typically have goodweatherability properties and may provide protection againstphotoyellowing when coated over a resinous substrate.

The good weatherability properties of polyesters containing resorcinolarylate units are believed to arise in large part from the screeningeffect said polymers may provide to ultraviolet (UV) light. On exposureto UV light polymers comprising resorcinol arylate chain members mayundergo photochemical Fries rearrangement converting at least a portionof the polymer from polyester chain members too-hydroxybenzophenone-type chain members. The o-hydroxybenzophenone-typechain members act to screen further UV light and protect UV-sensitivecomponents in a resorcinol arylate-containing composition. The goodweatherability properties of polymers comprising resorcinol arylatechain members make them especially useful in blends and in multilayerarticles in which said polymers may act as a protecting layer for moresensitive substrate components.

Copolyesters comprising resorcinol iso- and terephthalate polyesterchain members in combination with diacid or diol alkylene chain members(so-called “soft-block” chain members) are disclosed in commonly ownedU.S. Pat. No. 5,916,997. These copolymers have excellent weatherabilityand flexibility. Copolyestercarbonates comprising resorcinol iso- andterephthalate polyester chain members in combination with carbonatechain members are disclosed in commonly owned, co-pending applicationSer. No. 09/416,529, filed Oct. 12, 1999. These copolymers haveexcellent weatherability and are compatible with polycarbonates inblends.

Polyesters containing resorcinol arylate chain members have beenprepared by melt methods as disclosed in U.S. Pat. No. 4,127,560 and inJapanese Kokai 1/201,326. The methods may provide polyesters containingisophthalate and terephthalate chain members but do not allow theincorporation of greater than 30 mole % terephthalate. In addition, thepolyesters obtained have unacceptable color.

Polyesters containing resorcinol arylate chain members have also beenprepared by an interfacial method. The interfacial method comprises asolvent mixture containing water and at least one organic solventsubstantially immiscible with water. According to U.S. Pat. No.3,460,961 and Eareckson, Journal of Polymer Science, vol. XL, pp.399-406 (1959), preparation of resorcinol arylate polyesters with amixture of iso- and terephthalate chain members is performed by aninterfacial method in water and a water-immiscible solvent such aschloroform or dichloromethane using 1:1 stoichiometric ratio ofresorcinol to either iso- or terephthaloyl dichloride; or a mixturethereof, in the presence of aqueous sodium hydroxide. The resorcinol iscombined with the aqueous sodium hydroxide before addition of acidchlorides, and the reaction is run at pH which is initially high butwhich decreases as the reaction proceeds. The molecular weight of thepolymers is not controlled. The method provides polymer with very highweight average molecular weight (Mw), making the polymer unsuitable forsome applications. Furthermore, the polymer has poor thermal stabilityand loses molecular weight upon thermal treatment.

Multilayer articles containing layers made from resorcinolarylate-containing polyester have been described by Cohen et al.,Journal of Polymer Science : Part A-1, vol. 9, 3263-3299 (1971) and inU.S. Pat. No. 3,460,961. The polyester was made either in solution or byan interfacial process. The solution method requires the use of astoichiometric amount of an organic base, such as a tertiary amine,which must be isolated and recovered for reuse in any economical,environmentally friendly process. Both methods produce thermallyunstable polyester which can only be applied by solution coatingfollowed by evaporation of the solvent to make a multilayer article.This solution coating method has numerous deficiencies, some of whichare mentioned in the Cohen et al. paper at page 3267: namely, thenecessity to use high priced and toxic solvents, the inherently lowconcentration of the arylate polymer in the solvent and the tendency ofthe solutions to gel. Accordingly, the described polyesters wereconsidered “unacceptable coating candidates”.

Japanese Kokai 1/199,841 discloses articles having a substrate layercomprising at least 90 mole percent poly(ethylene terephthalate) and agas barrier coating layer which is a polyester of resorcinol and aminimum of 50 mole % isophthalic acid, optionally with copolyester unitsderived from another dicarboxylic acid such as terephthalic acid,naphthalenedicarboxylic acid or various other specifically nameddicarboxylic acids. The disclosed articles may be prepared by a seriesof operations including co-injection molding. However, the only types ofarticles disclosed are bottles, which are produced from a co-injectionmolded parison by subsequent blow molding. Larger articles, such asexternal automobile body parts, are not disclosed and no method fortheir production is suggested, nor are articles in which the substratelayer is anything other than poly(ethylene terephthalate). In addition,the resorcinol isophthalate polyesters were prepared either by meltmethods which do not allow the incorporation of greater than 30 mole %terephthalate and give polyester with unacceptable color, or by theinterfacial method which produces thermally unstable polyester.

It remains of interest, therefore, to develop a method for preparingweatherable, solvent resistant multilayer articles which are capable ofuse for such varied purposes as body parts for outdoor vehicles anddevices such as automobiles. There is also a particular need forpolymers comprising resorcinol arylate chain members having controlledmolecular weight, high thermal stability, and low color. There is also aparticular need for polymers comprising resorcinol arylate chain membersthat can be processed using typical melt processing techniques.

BRIEF SUMMARY OF THE INVENTION

The present inventors have identified the primary source of poor thermalstability in polymers comprising resorcinol arylate polyester chainmembers prepared by the interfacial method, and have discovered a methodto prepare said polymers in thermally stable form with controlledmolecular weight. The new method also allows the preparation ofvirtually colorless polymers comprising resorcinol arylate polyesterchain members.

In one of its aspects the present invention provides a compositioncomprising (a) a thermally stable polymer comprising resorcinol arylatepolyester chain members substantially free of anhydride linkages linkingat least two mers of the polymer chain, and (b) at least one auxiliarystabilizer additive selected from the group consisting of2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.

In another of its aspects the present invention provides a compositioncomprising (a) a thermally stable polymer consisting essentially ofresorcinol arylate polyester chain members substantially free ofanhydride linkages linking at least two mers of the polymer chain, and(b) at least one auxiliary stabilizer additive selected from the groupconsisting of 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.

In another of its aspects the present invention provides a compositioncomprising (a) a thermally stable copolymer comprising resorcinolarylate polyester chain members in combination with C₃₋₂₀ straight chainalkylene, C₃₋₁₀ branched alkylene, or C₄₋₁₀ cyclo- or bicyclo-alkylenechain members, substantially free of anhydride linkages linking at leasttwo mers of the polymer chain, and (b) at least one auxiliary stabilizeradditive selected from the group consisting of2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.

In another of its aspects the present invention provides a compositioncomprising (a) a thermally stable block copolymer comprising resorcinolarylate polyester segments in combination with organic carbonatesegments, substantially free of anhydride linkages linking at least twomers of the polymer chain, and (b) at least one auxiliary stabilizeradditive selected from the group consisting of2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.

In yet another of its aspects the present invention provides articlescomprising (a) a thermally stable polymer comprising resorcinol arylatepolyester chain members substantially free of anhydride linkages linkingat least two mers of the polymer chain, and (b) at least one auxiliarystabilizer additive selected from the group consisting of2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph of delta E vs. exposure in CIRA/sodalime xenon arclamp for a molded disk containing UVINUL 3030 and a resorcinol arylateblock copolymer with bisphenol A polycarbonate containing about 10 wt. %carbonate units, the disk comprising a layer of copolymer laminated ontoa layer of white bisphenol A polycarbonate.

FIG. 2 shows a graph of delta E vs. exposure in boro/boro xenon arc lampfor a molded disk containing CYASORB UV-3638 and a resorcinol arylateblock copolymer with bisphenol A polycarbonate containing about 20 wt. %carbonate units, the disk comprising a layer of copolymer laminated ontoa layer of white bisphenol A polycarbonate.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment the present invention comprises an interfacial methodfor preparing thermally stable polymers comprising resorcinol arylatepolyester chain members which derive their thermal stability in largepart from being substantially free of anhydride linkages in the polymerchains. In another embodiment the present invention comprises thethermally stable polymers prepared by such an interfacial method.

Thermal stability within the context of the present invention refers toresistance of a polymer to molecular weight degradation under thermalconditions. Thus, a polymer with poor thermal stability showssignificant molecular weight degradation under thermal conditions, suchas during extrusion, molding, thermoforming, hot-pressing, and likeconditions. Molecular weight degradation may also be manifest throughcolor formation and/or in the degradation of other properties such asweatherability, gloss, mechanical properties, and/or thermal properties.Molecular weight degradation can also cause significant variation inprocessing conditions as the melt viscosity changes.

In one of its aspects the method of the present invention providesthermally stable polymers comprising arylate polyester chain members.Said chain members comprise at least one diphenol residue in combinationwith at least one aromatic dicarboxylic acid residue. In one embodimentthe diphenol residue is derived from a 1,3-dihydroxybenzene moiety, asillustrated in Formula I, commonly referred to throughout thisspecification as resorcinol or resorcinol moiety. Resorcinol orresorcinol moiety as used within the context of the present inventionshould be understood to include both unsubstituted 1,3-dihydroxybenzeneand substituted 1,3-dihydroxybenzenes unless explicitly statedotherwise.

In Formula I R is at least one of C₁₋₁₂ alkyl or halogen, and n is 0-3.

Suitable dicarboxylic acid residues include aromatic dicarboxylic acidresidues derived from monocyclic moieties. In various embodimentssuitable dicarboxylic acid residues include those derived fromisophthalic acid, terephthalic acid, or mixtures of isophthalic andterephthalic acids. Suitable dicarboxylic acid residues also includethose derived from polycyclic moieties, illustrative examples of whichinclude diphenyl dicarboxylic acid, diphenylether dicarboxylic acid, andnaphthalenedicarboxylic acid, especially naphthalene-2,6-dicarboxylicacid. In some embodiments the aromatic dicarboxylic acid residues arederived from mixtures of isophthalic and/or terephthalic acids astypically illustrated in Formula II.

Therefore, in one embodiment the present invention provides thermallystable polymers comprising resorcinol arylate polyester chain members astypically illustrated in Formula III wherein R and n are as previouslydefined:

Previous interfacial methods for preparing polyesters comprisingresorcinol arylate chain members typically provide polymers with poorthermal stability and uncontrolled molecular weight. The presentinventors have discovered that a primary reason for poor thermalstability is the presence of anhydride linkages in the backbone of thepolyester chain. Typical anhydride linkages are illustrated in FormulaIV. Such anhydride linkages link at least two mers in a polymer chainand may arise through combination of two isophthalate or terephthalatemoieties or mixtures thereof, although it is to be understood thatanhydride linkages in polymers comprising resorcinol arylate chainmembers may arise through combination of any suitable similardicarboxylic acid residues or mixtures of suitable dissimilardicarboxylic acid residues present in a reaction mixture.

Although the invention is not limited by theory, it is believed that theanhydride linkage represents a weak bond in the polyester chain, whichcan break under thermal processing conditions to produce shorter chainsterminated by acid end-groups. These acid end-groups, in turn, mayaccelerate the hydrolysis of the arylate moiety, generating additionalcarboxyl and hydroxyl end-groups, and further contributing to themolecular weight degradation, and loss in other desirable properties.Anhydride linkages may arise through several mechanisms. In onemechanism a carboxylic acid chloride may be hydrolyzed to carboxylicacid when the esterification reaction is run at high pH. The carboxylicacid or corresponding carboxylate may then react with another carboxylicacid chloride to yield an anhydride linkage.

Anhydride linkages may be detected by means known to those skilled inthe art such as by ¹³C nuclear magnetic resonance spectroscopy (NMR).For example, resorcinol arylate polyesters comprising dicarboxylic acidresidues derived from a mixture of iso- and terephthalic acids typicallyshow ¹³C NMR resonances attributed to anhydride at 161.0 and 161.1 ppm(in deuterochloroform relative to tetramethylsilane), as well asresonances for the polymer carboxylic acid and hydroxyl end-groups.After thermal processing (for example, extrusion and/or molding), thepolymer molecular weight decreases, and the anhydride resonancestypically decrease, while those of the acid and hydroxyl end-groupstypically increase.

Anhydride linkages in polymers comprising resorcinol arylate polyesterchain members may also be detected by reaction of polymer with anucleophile, such as a secondary amine. For example, resorcinol arylatepolyesters comprising dicarboxylic acid residues derived from a mixtureof iso- and terephthalic acids can be dissolved in a convenient solvent,such as dichloromethane, and treated with a secondary amine, such asdibutylamine or diisobutylamine, for several minutes at ambienttemperature. Comparison of the starting polymer molecular weight to thatafter amine treatment typically shows a decrease in molecular weightwhich can be correlated with the corresponding decrease observed undertypical thermal processing conditions. Although the invention is notmeant to be limited by theory, it is believed that nucleophiles, such assecondary amine and phenolic, attack anhydride linkages (as opposed toester linkages) selectively under the reaction conditions. The decreasein molecular weight upon reaction with amine nucleophile is therefore anindication of the presence of anhydride functionality in the polymer.

In one of its aspects the present invention provides an interfacialmethod for preparing polymers comprising resorcinol arylate polyesterchain members substantially free of anhydride linkages, said methodcomprising a first step of combining at least one resorcinol moiety andat least one catalyst in a mixture of water and at least one organicsolvent substantially immiscible with water. Suitable resorcinolmoieties comprise units of Formula V:

wherein R is at least one of C₁₋₁₂ alkyl or halogen, and n is 0-3. Alkylgroups, if present, are typically straight-chain, branched, or cyclicalkyl groups, and are most often located in the ortho position to bothoxygen atoms although other ring locations are contemplated. SuitableC₁₋₁₂ alkyl groups include, but are not limited to, methyl, ethyl,n-propyl, isopropyl, butyl, iso-butyl, t-butyl, hexyl, cyclohexyl,nonyl, decyl, and aryl-substituted alkyl, including benzyl. In aparticular embodiment an alkyl group is methyl. Suitable halogen groupsare bromo, chloro, and fluoro. The value for n in various embodimentsmay be 0-3, in some embodiments 0-2, and in still other embodiments 0-1.In one embodiment a resorcinol moiety is 2-methylresorcinol. In anotherembodiment the resorcinol moiety is an unsubstituted resorcinol moietyin which n is zero.

The method further comprises combining at least one catalyst with thereaction mixture. Said catalyst may be present in various embodiments ata total level of 0.1 to 10 mole %, and in some embodiments at a totallevel of 0.2 to 6 mole % based on total molar amount of acid chloridegroups. Suitable catalysts comprise tertiary amines, quaternary ammoniumsalts, quaternary phosphonium salts, hexaalkylguanidinium salts, andmixtures thereof. Suitable tertiary amines include triethylamine,dimethylbutylamine, diisopropylethylamine,2,2,6,6-tetramethylpiperidine, and mixtures thereof. Other contemplatedtertiary amines include N-C₁-C₆-alkyl-pyrrolidines, such asN-ethylpyrrolidine, N-C₁-C₆-piperidines, such as N-ethylpiperidine,N-methylpiperidine, and N-isopropylpiperidine, N-C₁-C₆-morpholines, suchas N-ethylmorpholine and N-isopropyl-morpholine, N-C₁-C₆-dihydroindoles,N-C₁-C₆-dihydroisoindoles, N-C₁-C₆-tetrahydroquinolines,N-C₁-C₆-tetrahydroisoquinolines, N-C₁-C₆-benzo-morpholines,1-azabicyclo-[3.3.0]-octane, quinuclidine,N-C₁-C₆-alkyl-2-azabicyclo-[2.2.1]-octanes,N-C₁-C₆-alkyl-2-azabicyclo-[3.3.1]-nonanes, andN-C₁-C₆-alkyl-3-azabicyclo-[3.3.1]-nonanes,N,N,N′,N′-tetraalkylalkylene-diamines, includingN,N,N′,N′-tetraethyl-1,6-hexanediamine. In various embodiments tertiaryamines are triethylamine and N-ethylpiperidine.

When the catalyst consists of at least one tertiary amine alone, thensaid catalyst may be present in one embodiment at a total level of 0.1to 10 mole %, in another embodiment at a total level of 0.2 to 6 mole %,in another embodiment at a total level of 1 to 4 mole %, and in stillanother embodiment at a total level of 2.5 to 4 mole % based on totalmolar amount of acid chloride groups. In one embodiment of the inventionall of the at least one tertiary amine is present at the beginning ofthe reaction before addition of dicarboxylic acid dichloride toresorcinol moiety. In another embodiment a portion of any tertiary amineis present at the beginning of the reaction and a portion is addedfollowing or during addition of dicarboxylic acid dichloride toresorcinol moiety. In this latter embodiment the amount of any tertiaryamine initially present with resorcinol moiety may range in oneembodiment from about 0.005 wt. % to about 10 wt. %, in anotherembodiment from about 0.01 to about 1 wt. %, and in still anotherembodiment from about 0.02 to about 0.3 wt. % based on total amine.

Suitable quaternary ammonium salts, quaternary phosphonium salts, andhexaalkylguanidinium salts include halide salts such astetraethylammonium bromide, tetraethylammonium chloride,tetrapropylammonium bromide, tetrapropylammonium chloride,tetrabutylammonium bromide, tetrabutylammonium chloride,methyltributylammonium chloride, benzyltributylammonium chloride,benzyltriethylammonium chloride, benzyltrimethylammonium chloride,trioctylmethylammonium chloride, cetyldimethylbenzylammonium chloride,octyltriethylammonium bromide, decyltriethylammonium bromide,lauryltriethylammonium bromide, cetyltrimethylammonium bromide,cetyltriethylammonium bromide, N-laurylpyridinium chloride,N-laurylpyridinium bromide, N-heptylpyridinium bromide,tricaprylylmethylammonium chloride (sometimes known as ALIQUAT 336),methyltri-C₈-C₁₀-alkyl-ammonium chloride (sometimes known as ADOGEN464), N,N,N′,N′,N′-pentaalkyl-alpha, omega-amine-ammonium salts such asdisclosed in U.S. Pat. No. 5,821,322; tetrabutylphosphonium bromide,benzyltriphenylphosphonium chloride, triethyloctadecylphosphoniumbromide, tetraphenylphosphonium bromide, triphenylmethylphosphoniumbromide, trioctylethylphosphonium bromide, cetyltriethylphosphoniumbromide, hexaalkylguanidinium halides, hexaethylguanidinium chloride,and the like, and mixtures thereof.

Organic solvents substantially immiscible with water include those whichin one embodiment are less than about 5 wt. %, and in another embodimentless than about 2 wt. % soluble in water under the reaction conditions.Suitable organic solvents include dichloromethane, trichloroethylene,tetrachloroethane, chloroform, 1,2-dichloroethane, toluene, xylene,trimethylbenzene, chlorobenzene, o-dichlorobenzene, and mixturesthereof. In a particular embodiment the solvent is dichloromethane.

Suitable dicarboxylic acid dichlorides may comprise aromaticdicarboxylic acid dichlorides derived from monocyclic moieties,illustrative examples of which include isophthaloyl dichloride,terephthaloyl dichloride, or mixtures of isophthaloyl and terephthaloyldichlorides. Suitable dicarboxylic acid dichlorides may also comprisearomatic dicarboxylic acid dichlorides derived from polycyclic moieties,illustrative examples of which include diphenyl dicarboxylic aciddichloride, diphenylether dicarboxylic acid dichloride, andnaphthalenedicarboxylic acid dichloride, especiallynaphthalene-2,6-dicarboxylic acid dichloride; or from mixtures ofmonocyclic and polycyclic aromatic dicarboxylic acid dichlorides. In oneembodiment the dicarboxylic acid dichloride comprises mixtures ofisophthaloyl and/or terephthaloyl dichlorides as typically illustratedin Formula VI.

Either or both of isophthaloyl and terephthaloyl dichlorides may bepresent. In some embodiments the dicarboxylic acid dichlorides comprisemixtures of isophthaloyl and terephthaloyl dichloride in a molar ratioof isophthaloyl to terephthaloyl of about 0.25-4.0:1; in otherembodiments the molar ratio is about 0.4-2.5:1; and in still otherembodiments the molar ratio is about 0.67-1.5:1.

The pH of the reaction mixture is maintained in some embodiments betweenabout 3 and about 8.5, and in other embodiments between about 5 andabout 8, throughout addition of the at least one dicarboxylic aciddichloride to the at least one resorcinol moiety. Suitable reagents tomaintain the pH include alkali metal hydroxides, alkaline earthhydroxides, and alkaline earth oxides. In some embodiments the reagentsare potassium hydroxide and sodium hydroxide. In a particular embodimentthe reagent is sodium hydroxide. The reagent to maintain pH may beincluded in the reaction mixture in any convenient form. In someembodiments said reagent is added to the reaction mixture as an aqueoussolution simultaneously with the at least one dicarboxylic aciddichloride.

The temperature of the reaction mixture may be any convenienttemperature that provides a rapid reaction rate and a resorcinolarylate-containing polymer substantially free of anhydride linkages.Convenient temperatures include those from about −20° C. to the boilingpoint of the water-organic solvent mixture under the reactionconditions. In one embodiment the reaction is performed at the boilingpoint of the organic solvent in the water-organic solvent mixture. Inanother embodiment the reaction is performed at the boiling point ofdichloromethane.

The total molar amount of acid chloride groups added to the reactionmixture is stoichiometrically deficient relative to the total molaramount of phenolic groups. Said stoichiometric ratio is desirable sothat hydrolysis of acid chloride groups is minimized, and so thatnucleophiles such as phenolic and/or phenoxide may be present to destroyany adventitious anhydride linkages, should any form under the reactionconditions. The total molar amount of acid chloride groups includes theat least one dicarboxylic acid dichloride, and any mono-carboxylic acidchloride chain-stoppers and any tri- or tetra-carboxylic acid tri- ortetra-chloride branching agents which may be used. The total molaramount of phenolic groups includes resorcinol moieties, and anymono-phenolic chain-stoppers and any tri- or tetra-phenolic branchingagents which may be used. The stoichiometric ratio of total phenolicgroups to total acid chloride groups is in one embodiment about1.5-1.01:1 and in another embodiment about 1.2-1.02:1.

The presence or absence of adventitious anhydride linkages followingcomplete addition of the at least one dicarboxylic acid dichloride tothe at least one resorcinol moiety will typically depend upon the exactstoichiometric ratio of reactants and the amount of catalyst present, aswell as other variables. For example, if a sufficient molar excess oftotal phenolic groups is present, anhydride linkages are often found tobe absent. In one embodiment a molar excess of at least about 1% and inanother embodiment a molar excess of at least about 3% of total amountof phenolic groups over total amount of acid chloride groups may sufficeto eliminate anhydride linkages under the reaction conditions. Whenanhydride linkages may be present, it is often desirable that the finalpH be greater than 7 so that nucleophiles such as phenolic, phenoxideand/or hydroxide may be present to destroy any adventitious anhydridelinkages. Therefore, in various embodiments the method of the inventionmay further comprise the step of adjusting the pH of the reactionmixture in one embodiment to between 7 and 12, in another embodiment tobetween 8 and 12, and in still another embodiment to between 8.5 and 12,following complete addition of the at least one dicarboxylic aciddichloride to the at least one resorcinol moiety. The pH may be adjustedby any convenient method; in one embodiment the pH is adjusted using anaqueous base such as aqueous sodium hydroxide.

Provided the final pH of the reaction mixture is greater than 7, themethod of the invention in another embodiment may further comprise thestep of stirring the reaction mixture for a time sufficient to destroycompletely any adventitious anhydride linkages, should any be present.The necessary stirring time will depend upon reactor configuration,stirrer geometry, stirring rate, temperature, total solvent volume,organic solvent volume, anhydride concentration, pH, and other factors.In some instances the necessary stirring time is essentiallyinstantaneous, for example within seconds of pH adjustment to above 7,assuming any adventitious anhydride linkages were present to begin with.For typical laboratory scale reaction equipment a stirring time may berequired in one embodiment of at least about 3 minutes, and in anotherembodiment of at least about 5 minutes. By this process nucleophiles,such as phenolic, phenoxide and/or hydroxide, may have time to destroycompletely any adventitious anhydride linkages, should any be present.

At least one chain-stopper (also referred to sometimes hereinafter ascapping agent) may also be present in the method and compositions of theinvention. A purpose of adding at least one chain-stopper is to limitthe molecular weight of polymer comprising resorcinol arylate polyesterchain members, thus providing polymer with controlled molecular weightand favorable processability. Typically, at least one chain-stopper isadded when the resorcinol arylate-containing polymer is not required tohave reactive end-groups for further application. In the absence ofchain-stopper resorcinol arylate-containing polymer may be either usedin solution or recovered from solution for subsequent use such as incopolymer formation which may require the presence of reactiveend-groups, typically hydroxy, on the resorcinol-arylate polyestersegments. A chain-stopper may be at least one of mono-phenoliccompounds, mono-carboxylic acid chlorides, and/or mono-chloroformates.Typically, the at least one chain-stopper may be present in quantitiesof 0.05 to 10 mole %, based on resorcinol moieties in the case ofmono-phenolic compounds and based on acid dichlorides in the casemono-carboxylic acid chlorides and/or mono-chloroformates.

Suitable mono-phenolic compounds include monocyclic phenols, such asphenol, C₁-C₂₂ alkyl-substituted phenols, p-cumyl-phenol,p-tertiary-butyl phenol, hydroxy diphenyl; monoethers of diphenols, suchas p-methoxyphenol. Alkyl-substituted phenols include those withbranched chain alkyl substituents having 8 to 9 carbon atoms, preferablyin which about 47 to 89% of the hydrogen atoms are part of methyl groupsas described in U.S. Pat. No. 4,334,053. For some embodiments amono-phenolic UV absorber is used as capping agent. Such compoundsinclude 4-substituted-2-hydroxybenzophenones and their derivatives, arylsalicylates, monoesters of diphenols, such as resorcinol monobenzoate,2-(2-hydroxyaryl)-benzotriazoles and their derivatives,2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and likecompounds. In some embodiments mono-phenolic chain-stoppers are phenol,p-cumylphenol, and resorcinol monobenzoate.

Suitable mono-carboxylic acid chlorides include monocyclic,mono-carboxylic acid chlorides, such as benzoyl chloride, C₁-C₂₂alkyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and mixtures thereof; polycyclic,mono-carboxylic acid chlorides, such as trimellitic anhydride chloride,and naphthoyl chloride; and mixtures of monocyclic and polycyclicmono-carboxylic acid chlorides. The chlorides of aliphaticmonocarboxylic acids with up to 22 carbon atoms are also suitable.Functionalized chlorides of aliphatic monocarboxylic acids, such asacryloyl chloride and methacryoyl chloride, are also suitable. Suitablemono-chloroformates include monocyclic, mono-chloroformates, such asphenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate, toluene chloroformate, and mixtures thereof.

A chain-stopper can be combined together with the resorcinol moieties,can be contained in the solution of dicarboxylic acid dichlorides, orcan be added to the reaction mixture after production of aprecondensate. If mono-carboxylic acid chlorides and/ormono-chloroformates are used as chain-stoppers, they are oftenintroduced together with dicarboxylic acid dichlorides. Thesechain-stoppers can also be added to the reaction mixture at a momentwhen the chlorides of dicarboxylic acid have already reactedsubstantially or to completion. If phenolic compounds are used aschain-stoppers, they can be added in one embodiment to the reactionmixture during the reaction, or, in another embodiment, before thebeginning of the reaction between resorcinol moiety and acid chloridemoiety. When hydroxy-terminated resorcinol arylate-containingprecondensate or oligomers are prepared, then chain-stopper may beabsent or only present in small amounts to aid control of oligomermolecular weight.

In another embodiment the invention may encompass the inclusion of atleast one branching agent such as a trifunctional or higher functionalcarboxylic acid chloride and/or trifunctional or higher functionalphenol. Such branching agents, if included, can typically be used inquantities of 0.005 to 1 mole %, based on dicarboxylic acid dichloridesor resorcinol moieties used, respectively. Suitable branching agentsinclude, for example, trifunctional or higher carboxylic acid chlorides,such as trimesic acid trichloride, cyanuric acid trichloride,3,3′,4,4′-benzophenone tetracarboxylic acid tetrachloride,1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromelliticacid tetrachloride, and trifunctional or higher phenols, such asphloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenyl methane,2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane,2,4-bis-(4-hydroxyphenylisopropyl)-phenol,tetra-(4-hydroxyphenyl)-methane,2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methyl phenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,tetra-(4-[4-hydroxyphenylisopropyl]-phenoxy)-methane,1,4-bis-[(4,4-dihydroxytriphenyl)methyl]-benzene. Phenolic branchingagents may be introduced first with the resorcinol moieties whilst acidchloride branching agents may be introduced together with aciddichlorides.

For some applications such as for copolymer formation the resorcinolarylate-containing polymer may remain in solution for subsequent processsteps. In other instances such as in the production of resorcinolarylate polyester the polymer will normally be isolated from solution.Therefore, in another embodiment of the invention the resorcinolarylate-containing polymer is recovered from the reaction mixture.Recovery methods are well known to those skilled in the art and mayinclude such steps as acidification of the mixture, for example withphosphorous acid; subjecting the mixture to liquid-liquid phaseseparation; washing the organic phase with water and/or a dilute acidsuch as hydrochloric acid or phosphoric acid; precipitating by usualmethods such as through treatment with water or anti-solventprecipitation with, for example, methanol, ethanol, and/or isopropanol;isolating the resulting precipitates; and drying to remove residualsolvents.

If desired, the resorcinol arylate polymers of the invention may be madeby the present method further comprising the addition of a reducingagent. Suitable reducing agents include, for example, sodium sulfite,sodium gluconate, or a borohydride, such as sodium borohydride. Whenpresent, any reducing agents are typically used in quantities of from0.25 to 2 mole %, based on moles of resorcinol moiety.

In one of its embodiments the invention comprises thermally stableresorcinol arylate polyesters made by the present method andsubstantially free of anhydride linkages linking at least two mers ofthe polyester chain. In a particular embodiment said polyesters comprisedicarboxylic acid residues derived from a mixture of iso- andterephthalic acids as illustrated in Formula VII:

wherein R is at least one of C₁₋₁₂ alkyl or halogen, n is 0-3, and m isat least about 8. In various embodiments n is zero and m is betweenabout 10 and about 300. The molar ratio of isophthalate to terephthalateis in one embodiment about 0.25-4.0:1, in another embodiment about0.4-2.5:1, and in still another embodiment about 0.67-1.5:1.Substantially free of anhydride linkages means that said polyesters showdecrease in molecular weight in one embodiment of less than 30% and inanother embodiment of less than 10% upon heating said polymer at atemperature of about 280-290° C. for five minutes.

The present invention also encompasses thermally stable copolymerscontaining segments comprising resorcinol arylate polyester chainmembers made by the present method and substantially free of anhydridelinkages linking at least two mers of the copolymer chain. Thus, inanother of its embodiments the present invention comprises thermallystable copolyesters comprising resorcinol arylate polyester chainmembers in combination with dicarboxylic acid or diol alkylene chainmembers (so-called “soft-block” segments), said copolyesters beingsubstantially free of anhydride linkages in the polyester segments.Substantially free of anhydride linkages means that the copolyestersshow decrease in molecular weight in one embodiment of less than 10% andin another embodiment of less than 5% upon heating said copolyester at atemperature of about 280-290° C. for five minutes. Related copolyesterscontaining soft-block segments are disclosed in commonly owned U.S. Pat.No. 5,916,997.

The term soft-block as used herein, indicates that some segments of thepolymers are made from non-aromatic monomer units. Such non-aromaticmonomer units are generally aliphatic and are known to impartflexibility to the soft-block-containing polymers. The copolymersinclude those comprising structural units of Formulas I, VIII, and IX:

wherein R and n are as previously defined, Z is a divalent aromaticradical, R² is a C₃₋₂₀ straight chain alkylene, C₃₋₁₀ branched alkylene,or C₄₋₁₀ cyclo- or bicycloalkylene group, and R³ and R⁴ eachindependently represent

wherein Formula IX contributes from about 1 to about 45 mole percent tothe ester linkages of the polyester. Additional embodiments of thepresent invention provide a composition wherein Formula IX contributesin various embodiments from about 5 to about 40 mole percent to theester linkages of the polyester, and in other embodiments from about 5to about 20 mole percent to the ester linkages of the polyester. Anotherembodiment provides a composition wherein R represents in one embodimentC₃₋₁₄ straight chain alkylene, or C₅₋₆ cycloalkylene, and in anotherembodiment R² represents C₃₋₁₀ straight-chain alkylene orC₆-cycloalkylene. Formula VIII represents an aromatic dicarboxylic acidresidue. The divalent aromatic radical Z in Formula VIII may be derivedin various embodiments from at least one of the suitable dicarboxylicacid residues as defined hereinabove, and in some embodiments at leastone of 1,3-phenylene, 1,4-phenylene, or 2,6-naphthylene. In variousembodiments Z comprises at least about 40 mole percent 1,3-phenylene. Invarious embodiments of copolyesters containing soft-block chain membersn in Formula I is zero.

In various embodiments copolyesters containing resorcinol arylate chainmembers are those comprising from about 1 to about 45 mole % sebacate orcyclohexane-1,4-dicarboxylate units. In a particular embodiment acopolyester containing resorcinol arylate chain members is onecomprising resorcinol isophthalate and resorcinol sebacate units inmolar ratio between 8.5:1.5 and 9.5:0.5. In one embodiment saidcopolyester is prepared using sebacoyl chloride in combination withisophthaloyl dichloride.

In another of its embodiments the present invention comprises thermallystable block copolyestercarbonates comprising resorcinolarylate-containing block segments in combination with organic carbonateblock segments. The segments comprising resorcinol arylate chain membersin such copolymers are substantially free of anhydride linkages.Substantially free of anhydride linkages means that thecopolyestercarbonates show decrease in molecular weight in oneembodiment of less than 10% and in another embodiment of less than 5%upon heating said copolyestercarbonate at a temperature of about280-290° C. for five minutes. Related block copolyestercarbonates aredisclosed in commonly owned, co-pending application Ser. No. 09/416,529,filed Oct. 12, 1999.

The block copolyestercarbonates include those comprising alternatingarylate and organic carbonate blocks, typically as illustrated inFormula X, wherein R and n are as previously defined, and R⁵ is at leastone divalent organic radical

The arylate blocks have a degree of polymerization (DP), represented bym, in one embodiment of at least about 4, in another embodiment of atleast about 10, in another embodiment of at least about 20 and in stillanother embodiment of about 30-150. The DP of the organic carbonateblocks, represented by p, is in one embodiment generally at least about10, in another embodiment at least about 20 and in still anotherembodiment about 50-200. The distribution of the blocks may be such asto provide a copolymer having any desired weight proportion of arylateblocks in relation to carbonate blocks. In general, the content ofarylate blocks is in one embodiment about 6-95% by weight, in anotherembodiment about 10-95% by weight, and in another embodiment about50-95% by weight. In some particular embodiments the content of arylateblocks in the copolymer is about 10-30% by weight, and in otherparticular embodiments about 75-95% by weight.

Although a mixture of iso- and terephthalate is illustrated in FormulaX, the dicarboxylic acid residues in the arylate blocks may be derivedfrom any suitable dicarboxylic acid residue, as defined hereinabove, ormixture of suitable dicarboxylic acid residues, including those derivedfrom aliphatic diacid dichlorides (so-called “soft-block” segments). Invarious embodiments n is zero and the arylate blocks comprisedicarboxylic acid residues derived from a mixture of iso- andterephthalic acid residues, wherein the molar ratio of isophthalate toterephthalate is in one embodiment about 0.25-4.0:1, in anotherembodiment about 0.4-2.5:1, and in still another embodiment about0.67-1.5:1.

In the organic carbonate blocks, each R⁵ is independently a divalentorganic radical. In various embodiments said radical comprises at leastone dihydroxy-substituted aromatic hydrocarbon, and at least about 60percent of the total number of R⁵ groups in the polymer are aromaticorganic radicals and the balance thereof are aliphatic, alicyclic, oraromatic radicals. Suitable R⁵ radicals include m-phenylene,p-phenylene, 4,4′-biphenylene, 4,4′-bi(3,5-dimethyl)-phenylene,2,2-bis(4-phenylene)propane,6,6′-(3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indan]) and similar radicalssuch as those which correspond to the dihydroxy-substituted aromatichydrocarbons disclosed by name or formula (generic or specific) in U.S.Pat. No. 4,217,438.

In some embodiments each R⁵ is an aromatic organic radical and in otherembodiments a radical of Formula XI:

wherein each A¹ and A² is a monocyclic divalent aryl radical and Y is abridging radical in which one or two carbon atoms separate A¹ and A².The free valence bonds in Formula XI are usually in the meta or parapositions of A¹ and A² in relation to Y. Compounds in which R⁵ hasFormula XI are bisphenols, and for the sake of brevity the term“bisphenol” is sometimes used herein to designate thedihydroxy-substituted aromatic hydrocarbons. It should be understood,however, that non-bisphenol compounds of this type may also be employedas appropriate.

In Formula XI, A¹ and A² typically represent unsubstituted phenylene orsubstituted derivatives thereof, illustrative substituents (one or more)being alkyl, alkenyl, and halogen (particularly bromine). In oneembodiment unsubstituted phenylene radicals are preferred. Both A¹ andA² are often p-phenylene, although both may be o- or m-phenylene or oneo- or m-phenylene and the other p-phenylene.

The bridging radical, Y, is one in which one or two atoms, separate A¹from A². In a particular embodiment one atom separates A¹ from A².Illustrative radicals of this type are —O—, —S—, —SO— or —SO₂—,methylene, cyclohexyl methylene, 2-[2.2.1]-bicycloheptyl methylene,ethylene, isopropylidene, neopentylidene, cyclohexylidene,cyclopentadecylidene, cyclododecylidene, adamantylidene, and likeradicals.

In some embodiments gem-alkylene (commonly known as “alkylidene”)radicals are preferred. Also included, however, are unsaturatedradicals. In some embodiments the preferred bisphenol is2,2-bis(4-hydroxyphenyl)propane (bisphenol-A or BPA), in which Y isisopropylidene and A¹ and A² are each p-phenylene. Depending upon themolar excess of resorcinol moiety present in the reaction mixture, R⁵ inthe carbonate blocks may at least partially comprise resorcinol moiety.In other words, in some embodiments of the invention carbonate blocks ofFormula X may comprise a resorcinol moiety in combination with at leastone other dihydroxy-substituted aromatic hydrocarbon.

Diblock, triblock, and multiblock copolyestercarbonates are encompassedin the present invention. The chemical linkages between blockscomprising resorcinol arylate chain members and blocks comprisingorganic carbonate chain members may comprise at least one of

(a) an ester linkage between a suitable dicarboxylic acid residue of anarylate moiety and an —O—R⁵—O— moiety of an organic carbonate moiety,for example as typically illustrated in Formula XII, wherein R⁵ is aspreviously defined:

and (b) a carbonate linkage between a diphenol residue of a resorcinolarylate moiety and a —(C═O)—O— moiety of an organic carbonate moiety asshown in Formula XIII, wherein R and n are as previously defined:

The presence of a significant proportion of ester linkages of the type(a) may result in undesirable color formation in thecopolyestercarbonates. Although the invention is not limited by theory,it is believed that color may arise, for example, when R⁵ in Formula XIIis bisphenol A and the moiety of Formula XII undergoes Friesrearrangement during subsequent processing and/or light-exposure. In oneembodiment the copolyestercarbonate is substantially comprised of adiblock copolymer with a carbonate linkage between resorcinol arylateblock and an organic carbonate block. In another embodiment thecopolyestercarbonate is substantially comprised of a triblockcarbonate-ester-carbonate copolymer with carbonate linkages between theresorcinol arylate block and organic carbonate end-blocks.

Copolyestercarbonates with at least one carbonate linkage between athermally stable resorcinol arylate block and an organic carbonate blockare typically prepared from resorcinol arylate-containing oligomersprepared by various embodiments of the invention and containing in oneembodiment at least one and in another embodiment at least twohydroxy-terminal sites. Said oligomers typically have weight averagemolecular weight in one embodiment of about 10,000 to about 40,000, andin another embodiment of about 15,000 to about 30,000. Thermally stablecopolyestercarbonates may be prepared by reacting said resorcinolarylate-containing oligomers with phosgene, at least one chain-stopper,and at least one dihydroxy-substituted aromatic hydrocarbon in thepresence of a catalyst such as a tertiary amine.

It is believed that the weatherability and certain other beneficialproperties of the polymers comprising resorcinol arylate polyester chainmembers of the invention are attributable, at least in part, to theoccurrence of thermally or photochemically induced Fries rearrangementof arylate blocks to yield o-hydroxybenzophenone moieties or analogsthereof which serve as stabilizers to UV radiation. More particularly,at least a portion of resorcinol arylate polyester chain members canrearrange to yield chain members with at least one hydroxy group orthoto at least one ketone group. Such rearranged chain members aretypically o-hydroxybenzophenone-type chain members comprising one ormore of the following structural moieties:

wherein R and n are as previously defined. Theo-hydroxy-benzophenone-type chain members resulting from rearrangementof resorcinol arylate chain members can be present in resorcinol arylatepolyesters and in resorcinol arylate polyester-containing copolymers,including resorcinol arylate-containing copolyestercarbonates andresorcinol arylate-containing copolyesters containing soft-blocks. It isalso contemplated to introduce moieties of the types illustrated inFormulas XIV, XV, and XVI via synthesis and polymerization ofappropriate monomers in both homopolymers and copolymers by the methodof the present invention. In one embodiment the present inventionprovides thermally stable polyesters, copolyestercarbonates, andcopolyesters comprising structural units represented by Formulas III andXIV, wherein the molar ratio of structural units represented by FormulaIII to structural units represented by Formula XIV ranges in oneembodiment from about 99:1 to about 1:1, and in another embodiment fromabout 99:1 to about 80:20.

The polymers and copolymers comprising thermnally stable resorcinolarylate polyester chain members may also be employed in blends with atleast one other polymer, especially polycarbonates (hereinaftersometimes designated “PC”), polyesters, copolyestercarbbnates,polyarylates, polyetherimides, polyphenylene ethers, and additionpolymers. Related blends are disclosed in commonly owned U.S. Pat. No.6,143,839.

The polycarbonates in the blend compositions of the invention are, forthe most part, similar in molecular structure to the carbonate blocks ofthe block copolyestercarbonate as described hereinabove, withbisphenol-A homo- and copolycarbonates generally being preferred in someembodiments. Polyesters are illustrated by poly(alkylenedicarboxylates), especially poly(ethylene terephthalate) (hereinaftersometimes designated “PET”), poly(1,4-butylene terephthalate)(hereinafter sometimes designated “PBT”), poly(trimethyleneterephthalate) (hereinafter sometimes designated “PTT”), poly(ethylenenaphthalate) (hereinafter sometimes designated “PEN”), poly(butylenenaphthalate) (hereinafter sometimes designated “PBN”),poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate) (hereinaftersometimes designated “PETG”), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate) (hereinaftersometimes designated “PCCD”), and especially poly(alkylenearenedioates), with poly(ethylene terephthalate) and poly(1,4-butyleneterephthalate) being preferred in some embodiments.

Copolyestercarbonates may also be used in blends with polymerscomprising resorcinol arylate polyester chain members. Such copolymerscomprise, in addition to the organic carbonate units, ester units suchas isophthalate and/or terephthalate. The copolyestercarbonates whichfind use in the blends of the instant invention and the methods fortheir preparation are well known in the art as disclosed in, forexample, U.S. Pat. Nos. 3,030,331; 3,169,121; 3,207,814; 4,194,038;4,156,069; 4,238,596; 4,238,597; 4,487,896; and 4,506,065.

Polyarylates that may be employed in blends include those known in theart. They often comprise structural units derived from aromaticdihydroxy compounds and aromatic dicarboxylic acid compounds describedherein as suitable for preparation of polycarbonates, polyesters, andcopolyestercarbonates. In various embodiments polyarylates comprisethose with structural units comprising the 1,3-dihydroxybenzene moietypresent in the arylate blocks of the copolyestercarbonates, those withstructural units comprising any organic dihydroxy compound added in thecarbonate block formation step in synthesis of saidcopolyestercarbonates, and those with structural units comprising bothof the aforementioned dihydroxy moieties. Illustrative examples includepolyarylates comprising terephthalate and/or isophthalate structuralunits in combination with one or more of unsubstituted resorcinol,substituted resorcinol, and bisphenol A. The polyetherimide resinsuseful with the present invention are generically known compounds whosepreparation and properties are described in U.S. Pat. Nos. 3,803,085 and3,905,942.

Suitable addition polymers include homopolymers and copolymers,especially homopolymers of alkenylaromatic compounds, such aspolystyrene, including syndiotactic polystyrene, and copolymers ofalkenylaromatic compounds with ethylenically unsaturated nitriles, suchas acrylonitrile and methacrylonitrile; dienes, such as butadiene andisoprene; and/or acrylic monomers, such as ethyl acrylate. These lattercopolymers include the ABS (acrylonitrile-butadiene-styrene) and ASA(acrylonitrile-styrene-alkyl acrylate) copolymers.

In another embodiment the invention encompasses blends of polymersand/or copolymers comprising thermally stable resorcinol arylatepolyester chain members with at least two other polymers. Said at leasttwo other polymers may comprise miscible, immiscible, and compatibilizedblends including, but not limited to, PC/ABS, PC/ASA, PC/PBT, PC/PET,PC/polyetherimide, polyester/polyetherimide, polyphenyleneether/polystyrene, polyphenylene ether/polyamide, and polyphenyleneether/polyester.

The blend compositions of the invention may be prepared by suchconventional operations as solvent blending and melt blending. In someembodiments blend preparation is by melt blending, illustrative examplesof which include extrusion. The blends may additionally containart-recognized additives including, but not limited to, pigments, dyes,impact modifiers, UV screeners, UV absorbers, flame retardants, fillers,stabilizers, heat stabilizers, color stabilizers, flow aids, esterinterchange inhibitors, and mold release agents. It is intended that theblend compositions include simple physical blends and any reactionproducts thereof, as illustrated, for example, bypolyester-polycarbonate transesterification products.

Proportions of the polymers comprising resorcinol arylate polyesterchain members in such blends are determined chiefly by the resultingproportions of arylate blocks, which most often comprise the activeweatherability-improving entities, typical proportions providing about10-50% by weight of arylate blocks in the blend. In blends where somedegree of incompatibility may exist between the polymers comprisingresorcinol arylate polyester chain members of the invention and thepolycarbonates, polyesters, or addition polymers with which they may becombined, said blends are sometimes not fully transparent. However,transparent blends may often be prepared, if desired, by adjusting thelength of the arylate blocks in the polymers comprising resorcinolarylate polyester chain members. The other properties of said blends aregenerally excellent.

Compositions comprising resorcinol arylate polyester chain members madeby various embodiments of the method of the invention typically havesignificantly lower color, both before and after thermal processing,than related compositions made by melt methods, interfacial methods, andsolution methods of the prior art. In particular, melt methods typicallyprovide resorcinol arylate polyester with tan to dark brown color whilethe present interfacial method provides very lightly colored oressentially colorless polyester. The present compositions may be used invarious applications, especially those involving outdoor use andstorage, and hence requiring resistance to weathering. Their lighttransmitting properties are often similar to those of polycarbonates.Thus, they are often substantially transparent and colorless, and mayoften be employed as substitutes for polycarbonates in the fabricationof transparent sheet material when improved weatherability is mandated.

In another embodiment the present invention comprises multilayerarticles comprising a substrate layer comprising at least onethermoplastic polymer, thermnoset polymer, cellulosic material, glass,ceramic, or metal, and at least one coating layer thereon, said coatinglayer comprising at least one auxiliary stabilizer additive and at leastone polymer comprising structural units derived from at least one1,3-dihydroxybenzene moiety and at least one aromatic dicarboxylic acidmoiety and prepared by methods embodied in the present invention. In thepresent context a multilayer article is one containing at least twolayers. In various embodiments a coating layer comprises at least onethermally stable polymer comprising resorcinol arylate polyester chainmembers substantially free of anhydride linkages linking at least twomers of the polymer chain. Optionally, the multilayer articles mayfurther comprise an interlayer, for example an adhesive interlayer,between any substrate layer and any thermally stable polymer coatinglayer. Multilayer articles of the invention include, but are not limitedto, those which comprise a substrate layer and a coating layer of saidthermally stable polymer; those which comprise a substrate layer with acoating layer of said thermally stable polymer on each side of saidsubstrate layer; and those which comprise a substrate layer and at leastone coating layer of said thermally stable polymer with at least oneinterlayer between a substrate layer and a coating layer. Any interlayermay be transparent, translucent, or opaque, and/or may contain anadditive, for example a colorant or decorative material such as metalflake. If desired, an overlayer may be included over the coating layerof thermally stable polymer, for example to provide abrasion or scratchresistance. The substrate layer, coating layer of thermally stablepolymer, and any interlayers or overcoating layers are often incontiguous superposed contact with one another.

Within the context of the present invention it should be understood thatany coating layer comprising a thermally stable polymer comprisingresorcinol arylate polyester chain members may also include polymercomprising o-hydroxy-benzophenone or analogous chain members resultingfrom Fries rearrangement of said resorcinol arylate chain members, forexample after exposure of said coating layer to UV-light. Typically, apreponderance of any polymer comprising o-hydroxy-benzophenone oranalogous chain members will be on that side or sides of said coatinglayer exposed to UV-light and will overlay in a contiguous superposedlayer or layers that polymer comprising unrearranged resorcinol arylatechain members. If it is worn away or otherwise removed, polymercomprising o-hydroxybenzophenone or analogous chain members is capableof regenerating or renewing itself from the resorcinolarylate-containing layer or layers, thus providing continuous protectionfor any UV-light sensitive layers.

It has been unexpectedly discovered that the presence of at least oneauxiliary stabilizer additive in a coating layer comprising a polymercomprising resorcinol arylate polyester chain members may have abeneficial effect on color and other properties despite the fact thatpolymers comprising resorcinol arylate polyester chain members and theirFries rearrangement products themselves protect against photoyellowing.In one embodiment an auxiliary stabilizer additive is at least one colorstabilizer additive. In another embodiment a stabilizer additive is anyadditive which provides one or both of lower initial color or additionalresistance to weathering, as measured for example by initial yellownessindex (YI), or by resistance to yellowing and change in color, whencompared to a similar coating without at least one stabilizer additive.In another embodiment a stabilizer additive is any additive whichprovides improved retention of molecular weight and/or melt viscosityafter thermal processing of a coating layer, when compared to a similarcoating without at least one stabilizer additive. In another particularembodiment the stabilizer additive comprises at least one auxiliarylight stabilizer additive, such as a UV absorber. In one embodiment thepresence of at least one auxiliary UV absorber as stabilizer additiveprovides additional resistance to weathering, for example as measured byinitial yellowness index (YI), or resistance to yellowing and change incolor, when compared to a similar coating without at least one auxiliaryUV absorber. Since resorcinol arylate-comprising polymers generate UVabsorber in situ, it is unexpected that the addition of auxiliarystabilizer additive such as a UV absorber would affect the amount ofcolor or yellowness generated.

In various embodiments the unexpected beneficial effect of at least onestabilizer additive in a polymer composition comprising resorcinolarylate polyester chain members is not limited to said polymer made byany particular method of preparation. Thus, the unexpected beneficialeffect of at least one stabilizer additive may be realized in oneembodiment in a coating layer composition comprising a polymercomprising resorcinol arylate polyester chain members; in anotherembodiment in a coating layer composition comprising a polymerconsisting essentially of resorcinol arylate polyester chain members; inanother embodiment in a coating layer composition comprising a copolymercomprising resorcinol arylate polyester chain members in combinationwith C₃₋₂₀ straight chain alkylene, C₃₋₁₀ branched alkylene, or C₄₋₁₀cyclo- or bicyclo-alkylene chain members; and in still anotherembodiment in a coating layer composition comprising a polymercomprising resorcinol arylate polyester chain members in combinationwith organic carbonate segments. Said polymer comprising resorcinolarylate polyester chain members may be made using any known methodincluding, but not limited to, those methods disclosed in U.S. Pat. Nos.5,916,997 and 6,369,170; and in application Ser. No. 09/368,705, filedAug. 5, 1999; application Ser. No. 09/416,529, filed Oct. 12, 1999;application Ser. No. 09/916,160, filed Jul. 26, 2001; application Ser.No. 10/000,913; filed Nov. 2, 2001; application Ser. No. 10/105,563,filed Mar. 25, 2002; application Ser. No. 10/105,565, filed Mar. 25,2002; and application Ser. No. (RD-29522), filed December, 2002. In aparticular embodiment the unexpected beneficial effect of at least onestabilizer additive may be realized in a coating layer compositioncomprising a polymer comprising resorcinol arylate polyester chainmembers, said polymer being made by an interfacial method comprising thesteps of: (a) combining at least one resorcinol moiety and at least onecatalyst in a mixture of water and at least one organic solventsubstantially immiscible with water; and (b) adding to the mixture from(a) at least one dicarboxylic acid dichloride while maintaining the pHbetween 3 and 8.5 through the presence of an acid acceptor, wherein thetotal molar amount of acid chloride groups is stoichiometricallydeficient relative to the total molar amount of phenolic groups.

In various embodiments the unexpected beneficial effect of at least onestabilizer additive in a polymer composition comprising resorcinolarylate polyester chain members is not limited to a coating layercomprising said polymer composition. Said benefit may also be obtainedin a polymer composition comprising resorcinol arylate polyester chainmembers when said composition is a part of a multilayer article otherthan or in addition to a coating layer, and when said compositioncomprises a unitary article rather than a layered article.

In various embodiments auxiliary stabilizer additives include thoseknown in the art which stabilize or improve a physical or opticalproperty of a polyester or polycarbonate or polyestercarbonate comparedto that property in the absence of said stabilizer. For example,illustrative UV absorbers include, but are not limited to,hydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines,cyanoacrylates, oxanilides, and benzoxazinones. In some particularembodiments illustrative UV absorbers include, but are not limited to,2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (sometimesknown as CYASORB 5411); 2-hydroxy-4-n-octyloxybenzophenone (sometimesknown as CYASORB 531);2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol(sometimes known as CYASORB 1164);2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (sometimes known asCYASORB UV-3638); and1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane(sometimes known as UVINUL 3030). In other particular embodiments UVabsorbers are 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) or1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.

Illustrative UV absorbers also include nano-size inorganic materialssuch as titanium oxide, cerium oxide, and zinc oxide, all with particlesize less than about 100 nanometers. Illustrative examples of stabilizeradditives also include carbodiumides, such asbis-(2,6-diisopropylphenyl)carbodiimide and polycarbodiimides; hinderedamine light stabilizers; hindered phenols; phosphites and phosphorousacid.

Illustrative examples of stabilizer additives also include moietieshaving more than one epoxy functionality therein. In some embodimentsillustrative examples stabilizer additives include moieties having twoepoxy functionalities therein. In other embodiments moieties having morethan one epoxy functionality therein have two terminal epoxyfunctionalities. In other embodiments moieties having more than oneepoxy functionality therein contain only carbon, hydrogen and oxygen,and have a molecular weight of below about 1000 to facilitate blendingin the composition. Examples of suitable epoxy compounds include, butare not limited to,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene di-epoxide,bisphenol diglycidyl ethers, diglycidyl adducts of amines and amides,diglycidyl adducts of carboxylic acids and the like. Particular epoxycompounds suitable for use in this invention include, but are notlimited to,3,4-epoxy-6-methylcyclohexylmethyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, 2,3-epoxy-cylcohexylmethyl-3′,4′-epoxy cyclohexanecarboxylate, 4-(3,4-epoxy-5-methylcyclohexyl) butyl-3′,4′-epoxycyclohexane carboxylate, 3,4-epoxy cyclohexyl ethylene oxide,bisphenol-A diglycidyl ether, tetrabromobisphenol-A diglycidyl ether,diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalicacid, epoxidized soybean oil, epoxidized linseed oil,bis-epoxycyclohexyl adipate, butadiene diepoxide, and epoxidizedpolybutadiene. In one particular embodiment a suitable epoxy compound is3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate commerciallyavailable as ERL-4221 epoxy from Union Carbide.

Other suitable stabilizer additives are known in the art and aredisclosed in standard reference works, an illustrative example of whichis “Plastics Additives Handbook”, 5th edition, edited by H. Zweifel,Hanser Publishers. In some embodiments mixtures of stabilizer additivesare particularly effective, especially mixtures of the abovementionedstabilizer additives.

The amount of any stabilizer additive employed is in one embodiment in arange between about 0.0005 wt. % and 10 wt. %, in another embodiment ina range between about 0.001 wt. % and about 10 wt. %, in anotherembodiment in a range between about 0.005 wt. % and about 8 wt. %, inanother embodiment in a range between about 0.03 wt. % and about 8 wt.%, in another embodiment in a range between about 0.1 wt. % and about 6wt. %, in another embodiment in a range between about 0.2 wt. % andabout 5 wt. %, in another embodiment in a range between about 0.5 wt. %and about 5 wt. %, in still another embodiment in a range between about1 wt. % and about 5 wt. %, and in still another embodiment in a rangebetween about 1 wt. % and about 3 wt. %, based on the combined weightsof stabilizer and polymer comprising resorcinol arylate polyester chainmembers in a coating layer. When at least one epoxide is employed asstabilizer additive, it may be employed in any effective amount, and inparticular embodiments in amounts in those ranges given for additiveshereinabove. In some other particular embodiments at least one epoxidestabilizer additive may be employed in a range of between about 0.01 wt.% and about 5 wt. %; in other particular embodiments in a range ofbetween about 0.02 wt. % and about 5 wt. %; in other particularembodiments in a range of between about 0.02 wt. % and about 3 wt. %;and in other particular embodiments in a range of between about 0.02 wt.% and about 2 wt. %; all percentages being based on the combined weightsof organic difunctional epoxide and polymer comprising resorcinolarylate polyester chain members in a coating layer.

When at least one epoxide is employed as stabilizer additive, then atleast one catalyst compound may optionally be present in the compositionin some embodiments of the invention. Suitable catalysts comprise saltsfree from direct carbon-phosphorus bonds and containing at least one ofalkali metal cations and alkaline earth metal cations and halide anions.It is apparent that this class contains a large number of compounds.They comprise alkali metal halides, alkali metal carboxylates, alkalimetal enolates, amine hydrohalides, alkali metal carbonates andquaternary ammonium halides. Illustrative compounds within this classinclude, but are not limited to, lithium fluoride, lithium iodide,potassium bromide, potassium iodide, sodium dihydrogen phosphate, sodiumacetate, sodium benzoate, sodium caproate, sodium stearate, sodiumascorbate, magnesium caproate and dodecyltrimethylammonium bromide.Salts of aliphatic carboxylic acids containing at least about 18 carbonatoms, especially the alkali metal stearates and preferably sodiumstearate, have certain advantages over the other catalysts employedaccording to the invention and are therefore often preferred. In thefirst place, their use permits extrusion of the polyester-difunctionalepoxide composition at substantially higher feed rates than those whichare effective in their absence. In the second place, they may suppressthe formation of acrolein, a by-product from glycidyl reagents. In thethird place, they may impart substantially less odor to the compositionthan certain other compounds useful as catalysts, especially amines.

The catalyst component can be present in the composition of the presentinvention in any effective amount. In some embodiments the catalyst ispresent in an amount ranging from about 0.01 to about 1 weight percent,and in other embodiments in an amount ranging from about 0.03 to about0.1 weight percent; all percentages being based on the combined weightsof organic difunctional epoxide and polymer comprising resorcinolarylate polyester chain members in a coating layer.

A stabilizer additive may be combined with coating layer using knownmethods. In one embodiment stabilizer additive is at least partiallydissolved in a solution with components of a coating layer, and a filmof coating layer comprising stabilizer additive is solvent cast. Inanother embodiment stabilizer additive is at least partially dissolvedin a solution and impregnated from said solution into solid or at leastpartially solid coating layer. In still another embodiment stabilizeradditive is combined with coating layer in a melt method such asco-extrusion. If desired, the stabilizer additive may be combined withcoating layer in the form of a solution of stabilizer additive, forexample in water or organic solvent. In one embodiment an aqueoussolution of phosphorous acid is employed as stabilizer additive.

The multilayer articles typically have outstanding initial gloss,improved initial color, weatherability, impact strength, and resistanceto organic solvents encountered in their final applications. Saidarticles may also be recyclable by reason of the compatibility of thediscrete layers therein.

The material of the substrate layer in the articles of this inventionmay be at least one thermoplastic polymer, whether addition orcondensation prepared. Thermoplastic polymers include, but are notlimited to, polycarbonates, particularly aromatic polycarbonates,polyacetals, polyarylene ethers, polyphenylene ethers, polyarylenesulfides, polyphenylene sulfides, polyimides, polyamideimides,polyetherimides, polyetherketones, polyaryletherketones,polyetheretherketones, polyetherketoneketones, polyamides, polyesters,liquid crystalline polyesters, polyetheresters, polyetheramides,polyesteramides, and polyestercarbonates (other than those employed forthe coating layer, as defined hereinafter). In some embodimentspolycarbonates and polyesters are preferred. A substrate layer mayadditionally contain art-recognized additives including, but not limitedto, colorants, pigments, dyes, impact modifiers, stabilizers, colorstabilizers, heat stabilizers, UV screeners, UV absorbers, flameretardants, fillers, flow aids, ester interchange inhibitors, and moldrelease agents.

Suitable polycarbonates include homopolycarbonates comprising structuralunits of the type described for the organic carbonate blocks in thecopolyestercarbonates of the invention. In some embodiments thepolycarbonates are bisphenol A homo- and copolycarbonates. In variousembodiments the weight average molecular weight of the initialpolycarbonate ranges from about 5,000 to about 100,000; in otherembodiments the weight average molecular weight of the initialpolycarbonate ranges from about 25,000 to about 65,000.

The polycarbonate substrate may also be a copolyestercarbonate (otherthan that copolyestercarbonate employed for the coating layer as definedhereinafter). Such copolymers typically comprise, in addition to theorganic carbonate units, ester units such as isophthalate and/orterephthalate. The copolyestercarbonates which find use as substrates inthe instant invention and the methods for their preparation are wellknown in the art as disclosed in, for example, U.S. Pat. Nos. 3,030,331;3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,238,596; 4,238,597;4,487,896; and 4,506,065.

Polyester substrates include, but are not limited to, poly(alkylenedicarboxylates), especially poly(ethylene terephthalate),poly(1,4-butylene terephthalate), poly(trimethylene terephthalate),poly(ethylene naphthalate), poly(butylene naphthalate),poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate). Alsoincluded are polyarylates as described hereinabove, illustrativeexamples of which include those comprising structural units derived frombisphenol A, terephthalic acid, and isophthalic acid.

Suitable addition polymer substrates include homo- and copolymericaliphatic olefin and functionalized olefin polymers (which arehomopolymers and copolymers comprising structural units derived fromaliphatic olefins or functionalized olefins or both), and their alloysor blends. Illustrative examples include, but are not limited to,polyethylene, polypropylene, thermoplastic polyolefin (“TPO”),ethylene-propylene copolymer, poly(vinyl chloride), poly(vinylchloride-co-vinylidene chloride), poly(vinyl fluoride), poly(vinylidenefluoride), poly(vinyl acetate), poly(vinyl alcohol), poly(vinylbutyral), poly(acrylonitrile), acrylic polymers such as those of(meth)acrylamides or of alkyl (meth)acrylates such as poly(methylmethacrylate) (“PMMA”), and polymers of alkenylaromatic compounds suchas polystyrenes, including syndiotactic polystyrene. In some embodimentsthe preferred addition polymers are polystyrenes and especially theso-called ABS and ASA copolymers, which may contain thermoplastic,non-elastomeric styrene-acrylonitrile side chains grafted on anelastomeric base polymer of butadiene and alkyl acrylate, respectively.

Blends of any of the foregoing polymers may also be employed assubstrates. Typical blends include, but are not limited to, thosecomprising PC/ABS, PC/ASA, PC/PBT, PC/PET, PC/polyetherimide,PC/polysulfone, polyester/polyetherimide, PMMA/acrylic rubber,polyphenylene ether-polystyrene, polyphenylene ether-polyamide orpolyphenylene ether-polyester. Although the substrate layer mayincorporate other thermoplastic polymers, the above-describedpolycarbonates and/or addition polymers often constitute the majorproportion thereof.

The substrate layer in the multilayer articles of this invention mayalso comprise at least one of any thermoset polymer. Suitable thermosetpolymer substrates include, but are not limited to, those derived fromepoxys, cyanate esters, unsaturated polyesters, diallylphthalate,acrylics, alkyds, phenol-formaldehyde, novolacs, resoles, bismaleimides,PMR resins, melamine-formaldehyde, urea-formaldehyde, benzocyclobutanes,hydroxymethylfurans, and isocyanates. In one embodiment of the inventionthe thermoset polymer substrate comprises a RIM material. In anotherembodiment of the invention the thermoset polymer substrate furthercomprises at least one thermoplastic polymer, such as, but not limitedto, polyphenylene ether, polyphenylene sulfide, polysulfone,polyetherimide, or polyester. Said thermoplastic polymer is typicallycombined with thermoset monomer mixture before curing of said thermoset.

In one embodiment of the invention a thermoplastic or thermosetsubstrate layer also incorporates at least one filler and/or pigment.Illustrative extending and reinforcing fillers, and pigments includesilicates, zeolites, titanium dioxide, stone powder, glass fibers orspheres, carbon fibers, carbon black, graphite, calcium carbonate, talc,mica, lithopone, zinc oxide, zirconium silicate, iron oxides,diatomaceous earth, calcium carbonate, magnesium oxide, chromic oxide,zirconium oxide, aluminum oxide, crushed quartz, calcined clay, talc,kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetictextile fibers, especially reinforcing fillers such as glass fibers,carbon fibers, and metal fibers, as well as colorants such as metalflakes, glass flakes and beads, ceramic particles, other polymerparticles, dyes and pigments which may be organic, inorganic ororganometallic. In another embodiment the invention encompassesmultilayer articles comprising a filled thermoset substrate layer suchas a sheet-molding compound (SMC).

The substrate layer may also comprise at least one cellulosic materialincluding, but not limited to, wood, paper, cardboard, fiber board,particle board, plywood, construction paper, Kraft paper, cellulosenitrate, cellulose acetate butyrate, and like cellulosic-containingmaterials. The invention also encompasses blends of at least onecellulosic material and either at least one thermoset polymer(particularly an adhesive thermoset polymer), or at least onethermoplastic polymer (particularly a recycled thermoplastic polymer,such as PET or polycarbonate), or a mixture of at least one thermosetpolymer and at least one thermoplastic polymer.

Multilayer articles encompassed by the invention also include thosecomprising at least one glass layer. Typically any glass layer is asubstrate layer, although multilayer articles comprising a thermallystable polymer coating layer interposed between a glass layer and asubstrate layer are also contemplated. Depending upon the nature ofcoating and glass layers, at least one adhesive interlayer may bebeneficially employed between any glass layer and any thermally stablepolymer coating layer. The adhesive interlayer may be transparent,opaque or translucent. For many applications it is preferred that theinterlayer be optically transparent in nature and generally have atransmission of greater than about 60% and a haze value less than about3% with no objectionable color.

Metal articles exposed to UV-light may exhibit tarnishing and otherdetrimental phenomena. In another embodiment the invention encompassesmultilayer articles comprising at least one metal layer as substratelayer. Representative metal substrates include those comprising brass,aluminum, magnesium, chrome, iron, steel, copper, and other metals oralloys or articles containing them, which may require protection fromUV-light or other weather phenomena. Depending upon the nature ofcoating and metal layers, at least one adhesive interlayer may bebeneficially employed between any metal layer and any thermally stablepolymer coating layer.

Also present in the articles of the invention is at least one coatinglayer comprising at least one polymer comprising structural unitsderived from at least one 1,3-dihydroxybenzene moiety and at least onearomatic dicarboxylic acid moiety prepared by methods embodied in thepresent invention. In various embodiments, suitable coating layerscomprise polymers comprising thermally stable resorcinol arylatepolyester chain members. In other embodiments suitable coating layerscomprise resorcinol arylate polyesters, copolyesters (particularly thosecontaining soft-blocks), copolyestercarbonates, and mixtures thereof.Copolyestercarbonates, when used in both substrate layer and in coatinglayer, are different from each other in molecular structure. Morespecifically, when the coating layer contains copolyestercarbonate withresorcinol arylate polyester blocks, then any ester blocks in thesubstrate copolyestercarbonate layer will typically be derived from thesame divalent organic radical as contained in the carbonate blocks.

It is also within the scope of the invention for other polymers to bepresent which are miscible in at least some proportions with a polymercoating layer comprising at least one thermally stable polymercomprising structural units derived from at least one1,3-dihydroxybenzene moiety and at least one aromatic dicarboxylic acidmoiety. Illustrative examples of at least partially miscible polymersinclude polyetherimide and polyesters such as PBT, PET, PTT, PEN, PBN,PETG, PCCD, and bisphenol A polyarylate. In one embodiment the coatinglayer polymer consists essentially of thermally stable resorcinolarylate polyesters, copolyesters, or copolyestercarbonates.

Another aspect of the invention is a method for preparing a multilayerarticle which comprises applying at least one thermally stable coatinglayer to a second layer, said second layer comprising at least onethermoplastic polymer, thermoset polymer, cellulosic material, glass, ormetal, and said coating layer comprising at least one polymer comprisingstructural units derived from at least one 1,3-dihydroxybenzene moietyand at least one aromatic dicarboxylic acid moiety, the polymer beingsubstantially free of anhydride linkages linking at least two mers ofthe polymer chain.

In one embodiment of the invention, at least one thermally stablecoating layer is applied to a second layer, which may be the substratelayer or at least one intermediate layer ultimately to be disposedbetween the coating and substrate layers. An intermediate layer maycomprise any of the materials suitable for use as the substrate orcoating layer, and may further contain fillers and colorants such asdescribed hereinabove. When necessary, it may be specifically chosen soas to provide good adhesion between substrate and coating layers.Colorants of the previously described types may also be present in thecoating layer.

In one embodiment application of the at least one coating layer may beperformed by solvent-casting. In another embodiment application of saidcoating layer comprises fabrication of a separate sheet thereof followedby application to the second layer, or by simultaneous production ofboth layers, typically in a melt process. Thus, there may be employedsuch methods as thermoforming, compression molding, co-injectionmolding, coextrusion, overmolding, blow molding, multi-shot injectionmolding and placement of a film of the coating layer material on thesurface of the second layer followed by adhesion of the two layers,typically in an injection molding apparatus; e.g., in-mold decoration,or in a hot-press. These operations may be conducted underart-recognized conditions.

It is also within the scope of the invention to apply a structurecomprising the coating layer and the second layer to a third, substratelayer, which may be, for example, of a thermoplastic, thermoset, orcellulosic material similar or identical to that of the second layer butdifferent from that of the coating layer. This may be achieved, forexample, by charging an injection mold with the structure comprising thecoating layer and the second layer and injecting the substrate sheetmaterial behind it. By this method, in-mold decoration and the like arepossible. Both sides of the substrate layer may receive the otherlayers, though in some embodiments it may be preferred to apply them toonly one side.

The thicknesses of the various layers in multilayer articles of thisinvention are most often as follows:

substrate—at least about 125μ (microns), or at least about 250μ, or atleast about 400μ,

coating—about 2-2,500, or about 10-250, or about 50-175μ,

second material, if any—about 2-2,500, or about 10-250, or about50-175μ,

total—at least about 125μ, or at least about 250μ, or at least about400μ.

The articles of this invention are typically characterized by the usualbeneficial properties of the substrate layer, in addition toweatherability as may be evidenced by such properties as improvedinitial gloss, improved initial color, improved resistance toultraviolet radiation and maintenance of gloss, improved impactstrength, and resistance to organic solvents encountered in their finalapplications. Depending upon such factors as the coating layer/substratecombination, the multilayer articles may possess recycling capability,which makes it possible to employ the regrind material as a substratefor further production of articles of the invention.

Multilayer articles which can be made which comprise thermally stablepolymers comprising resorcinol arylate polyester chain members includeaircraft, automotive, truck, military vehicle (including automotive,aircraft, and water-borne vehicles), scooter, and motorcycle exteriorand interior components, including panels, quarter panels, rockerpanels, trim, fenders, doors, decklids, trunklids, hoods, bonnets,roofs, bumpers, fascia, grilles, mirror housings, pillar appliques,cladding, body side. moldings, wheel covers, hubcaps, door handles,spoilers, window frames, headlamp bezels, headlamps, tail lamps, taillamp housings, tail lamp bezels, license plate enclosures, roof racks,and running boards; enclosures, housings, panels, parts, and trim foroutdoor vehicles and devices; enclosures for electrical andtelecommunication devices; outdoor furniture; aircraft components; boatsand marine equipment, including trim, enclosures, and housings; outboardmotor housings; depth finder housings, personal water-craft; jet-skis;pools; spas; hot-tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, countertops, windows, window trim,floors, decorative window furnishings or treatments; treated glasscovers for pictures, paintings, posters, and like display items; opticallenses; ophthalmic lenses; corrective ophthalmic lenses; implantableophthalmic lenses; refractors; sheaths for fluorescent tubes; sleeveguards; wall panels, doors and door trim; counter tops; protectedgraphics; outdoor and indoor signs; enclosures, housings, panels, andparts for automatic teller machines (ATM); enclosures, housings, panels,and parts for lawn and garden tractors, lawn mowers, and tools,including lawn and garden tools; window and door trim; sports equipmentand toys; enclosures, housings, panels, and parts for snowmobiles;recreational vehicle panels and components; playground equipment; shoelaces; articles made from plastic-wood combinations; golf coursemarkers; utility pit covers; computer housings; desk-top computerhousings; portable computer housings; lap-top computer housings;palm-held computer housings; monitor housings; printer housings;keyboards; FAX machine housings; copier housings; telephone housings;phone bezels; mobile phone housings; radio sender housings; radioreceiver housings; light fixtures; lighting appliances; networkinterface device housings; transformer housings; air conditionerhousings; cladding or seating for public transportation; cladding orseating for trains, subways, or buses; meter housings; antenna housings;cladding for satellite dishes; coated helmets and personal protectiveequipment; coated synthetic or natural textiles; coated photographicfilm and photographic prints; coated painted articles; coated dyedarticles; coated fluorescent articles; coated foam articles; and likeapplications. The invention further contemplates additional fabricationoperations on said articles, such as, but not limited to molding,in-mold decoration, baking in a paint oven, lamination, and/orthermoforming.

The invention is illustrated by the following, non-limiting examples.All parts are by weight unless otherwise designated. Molecular weightvalues for polymeric samples were determined by gel permeationchromatography (GPC) using 3% isopropanol/chloroform eluent at 0.75milliliters (ml) per minute (min) on a Polymer Labs Mixed C sizeexclusion column held at 35° C., and calibrated using polystyrenestandards, and analyzed with Turbogel software.

EXAMPLE 1

This example illustrates the preparation of a thermally stableresorcinol arylate polyester with both iso- and terephthalate units. Toa one liter, five neck, Morton flask blanketed with nitrogen andequipped with a mechanical stirrer, pH electrode, reflux condenser, twopressure equalizing addition funnels, was charged resorcinol (21.8 grams[g]; 0.198 moles [mol]), resorcinol monobenzoate capping agent (1.07 g;2.5 mole %), triethylamine (0.274 ml; 1 mole %), dichloromethane (150ml), and water (100 ml). One addition funnel was charged with sodiumhydroxide pellets (16.84 g; 0.42 mol) and water (32 ml), while asolution of isophthaloyl dichloride (20.3 g; 0.1 mol), terephthaloyldichloride (20.3 g; 0.1 mol), and dichloromethane (150 ml) was added tothe second. The pH of the reaction mixture was adjusted to 7.5 withsodium hydroxide prior to the addition of acid chloride solutions, whichwere added over 6 minutes. The pH of the reaction was maintained between7.25 and 7.75 for the first ten minutes of reaction. At 11 minutes thereaction the pH was raised to about 10 with the addition of sodiumhydroxide and held for an additional minutes. The stirring was stoppedand the aqueous layer was removed. The resulting gray organic layer waswashed with IN hydrochloric acid, 0.1N hydrochloric acid, water (threetimes), and the polymer isolated by precipitation into boiling wateryielding a white, fibrous material which was dried in vacuum at 110° C.overnight. The isolated polymer was the desired resorcinol arylatepolyester.

CONTROL EXAMPLE 1

A polyester of resorcinol with a mixture of iso- and terephthalate wasprepared in a blender according to the interfacial method of U.S. Pat.No. 3,460,961. The isolated polymer had weight average molecular weightof about, 289,000. The procedure was modified by addition of 4 mole %chain-stopper (phenol), resulting in polymer with weight averagemolecular weight of about 51,000.

CONTROL EXAMPLE 2

A polyester of resorcinol with a mixture of iso- and terephthalate wasprepared according to the solution method of Cohen et al., Journal ofPolymer Science: Part A-1, vol. 9, 3263-3299 (1971). To a one-liter,three neck, round bottomed flask equipped with a mechanical stirrer andan addition funnel were charged isophthaloyl dichloride (5.076 g, 25millimoles [mmol]), terephthaloyl dichloride (5.076 g, 25 mmol),resorcinol (5.506 g, 50 mmol), and tetrahydrofuran (200 ml) dried bydistillation from sodium and benzophenone. Polymerization was initiatedby dropwise addition of a stoichiometric amount of triethylamine (10.12g, 10 mmol) over 30 minutes. The mixture then was stirred for 3 hours atroom temperature. Triethylamine hydrochloride was removed from thereaction mixture by filtration. The filtrate was slowly poured intomethanol (500 ml) in a blender. The precipitated polymer was washed withhot water and dried in a vacuum oven. The isolated polymer had weightaverage molecular weight of about 47,000.

EXAMPLES 2-11

These examples illustrate the preparation of hydroxy-terminatedresorcinol iso/terephthalate oligomers. Into a 1 liter Morton flaskequipped with a mechanical stirrer, pH electrode, condenser, and twoaddition tubes connected to metering pumps were charged resorcinot(12.11 g, 0.11 mol), water (18 ml), methylene chloride (200 ml), andtriethylamine (140 to 560 microliters, 1 to 4 mol % based on acidchlorides). The mixture was stirred at 500 rpm. A two-step additionprofile was used for the delivery of acid chloride solution and basesolution. In the first step, a majority of base (60 to 80% out of totalbase amount of 17.5 ml of 33% aqueous sodium hydroxide solution) and thewhole acid chloride solution (70 ml solution of isophthaloyl dichloride(10.15 g, 0.05 mol) and terephthaloyl dichloride (10.15 g, 0.05 mol) inmethylene chloride) were added at constant rates, and the remaining basewas added in the second step at continuously decreasing rate. The basewas pumped from graduated burettes and the amount was checked every 30seconds in order to control the stoichiometry. The pH varied betweenabout 3.5 and about 8. The length of the first step was varied from 7 to13 minutes with the total step 1 and step 2 time constant at 25 minutes.The reaction mixture was further stirred for 30 minute total reactiontime. The reaction conditions and weight average molecular weights ofthe isolated polymers are shown in Table 1.

TABLE I Base % Base Addition Added in time mol % Oligomer Example 1stStep (min.) triethylamine Mw^(a) 2 60  7 1   27.3 3 60  7 4   26.9 4 6013 4   24.5 5 60 13 1   26   6 70 10 2.5 28.3 7 70 10 2.5 23   8 80  74   28.4 9 80  7 1   30.8 10  80 13 4   29.5 11  80 13 1   30.4^(a)times 10⁻³

A sample of each polymer was analyzed for anhydride content by treatmentin solution with diisobutylamine. Polymers prepared using 4 mol %triethylamine showed greater than 95% retention of weight averagemolecular weight.

EXAMPLES 12-28

The procedure of Examples 2-11 was repeated except that in someexperiments 13 to 15 mol % total excess of resorcinol was used. In someexperiments a small amount of capping agent (1 mol % phenol) was added.In some cases; the reaction mixture was heated externally to a refluxingpoint at 3 minutes. The reaction conditions and weight average molecularweights of the isolated polymers are shown in Table 2.

TABLE 2 mol % Initial % Mw Example triethylamine Comments^(a) Reflux^(b)Mw^(c) Retention^(d) 12 4 1% PhOH Y 19.5 99   13 4 15% excess Rs N 19.9100   14 4 0.5% PhOH N 21.6 99.5 15 4 15% excess Rs Y 21.8 96.6 16 4 1%PhOH N 21.9 99.3 17 4 1% PhOH Y 22.2 97.7 18 4 N 22.3 96.1 19 4 13%excess Rs N 22.4 97.7 20 4 1% PhOH Y 22.4 96.4 21 4 1% PhOH Y 22.5 93  22 4 1% PhOH N 22.7 97.8 23 4 0.5 PhCOCl N 24.6 99   24   2.5 1% PhOH Y24.7 97.2 25 4 N 24.8 96.7 26 4 Y 25.3 98   27 4 N 26.6 97.7 28 3 Y 30.3100   ^(a)PhOH (phenol); Rs (resorcinol); PhCOCl (benzoyl chloride)^(b)Y (Yes); N (No) ^(c)times 10⁻³ ^(d)following treatment withdiisobutylamine in solution

EXAMPLES 29-46

The procedure of Examples 2-11 was repeated except that a portion oftertiary amine was added following addition of dicarboxylic aciddichloride to resorcinol moiety. A total of 4 mol % tertiary amine(40000 ppm; based on moles acid clorides) was added. The reactionconditions and weight average molecular weights of the isolated polymersare shown in Table 3. Example 46 is a control experiment in which allthe tertiary amine was present at the beginning of the reaction beforeaddition of dicarboxylic acid dichloride to resorcinol moiety

TABLE 3 Base TEA % Base Addition added Added in time initially Initial %Mw Example 1st Step (min.) (ppm) Mw^(a) Retention^(b) 29 80  7 50 29.396.5 30 80  7 10 23.1 86.8 31 80  7 10 22.2 98.5 32 80  7 50 29.4 97.433 96  7 10 32.7 94.3 34 96  7 50 34.4 92.5 35 88 10 30 26.5 99.4 36 8810 30 25.6 101   37 80 13 50 25.9 95.9 38 80 13 10 25.2 96.6 39 96 13 5029.4 90.2 40 96 13 10  22.14  98.59 41 96 13 50 26.7  92.93 42 96 13 1023.6 90.5 43 96 16 10  21.6,  98.8, 22.0 98.0 44 96 19 10  24.1,  95.9,22.3 97.3 45 64  7 10   21.46,  96.3,  23.31 100   46 96 16 40000   24.7,  92.7, 23.1 94.4 ^(a)times 10⁻³ ^(b)following treatment withdiisobutylamine in solution

EXAMPLE 47

This example illustrates the preparation of a thermally stableresorcinol iso/terephthalate-block-copolycarbonate beginning with thepreparation of hydroxy-terminated resorcinol iso/terephthalate oligomer.To a thirty liter glass reactor equipped with a glass impeller,centrifuge recirculation pump, reflux condenser andpressure-equilibration addition funnel were charged resorcinol (605.6 g,5.5 mol), methyltributylammonium chloride (82.5 g of a 75 wt. % aqueoussolution; 0.275 mol), dichloromethane (6.5 liters), and water (2.5liters). The recirculation pump was turned on and the mixture wasdegassed with nitrogen while stirring. The pH of the aqueous phase wasadjusted to 7 with 50% aqueous sodium hydroxide solution. Reaction wascarried out by adding a solution of acid chlorides (507.5 g each of iso-and terephthaloyl dichlorides; 5.00 moles total in 2.0 liters ofdichloromethane solution) while stirring and simultaneously adding 50%sodium hydroxide solution at such a rate that the pH was maintainedbetween 6 and 8. The acid chlorides were added using a three-stepprogram with the rate of addition declining with each step. A timer wasstarted at the beginning of acid chloride addition. The pH wasmaintained at 8 while adding acid chlorides over 8 minutes using thefollowing protocol: 40% of total acid chlorides was added over the first2 minutes; 30% of total was added over the next 2 minutes; the remaining30% of total was added over the next 4 minutes. The recirculation loopwas running during the entire time.

Following complete addition of acid chlorides, the pH was slowly raisedto 11-12 over two to three minutes, and the reaction mixture was stirredfor 10 minutes. The polymer formed was a hydroxy-terminated oligomerwith weight average molecular weight (Mw) of approximately 20,000.

Bisphenol A (1102 g, 4.83 mol), dichloromethane (4.0 liters),triethylamine (17 ml, 0.12 mol), p-cumyl phenol capping agent (60 g),and water (6.0 liters) were then added and the recirculation loop wasturned on. Phosgene was introduced at pH 7.5-8.5, then increasing slowlyto pH 10-10.5 using a 15% excess over the theoretical amount ofphosgene.

The reaction mixture was separated, the organic phase washed with 1Nhydrochloric acid, 0.1N hydrochloric acid, and twice with water, and thepolymer was isolated by precipitation in methanol. The polymer obtainedwas the desired resorcinol iso/terephthalate-co-BPA polycarbonatecopolymer.

EXAMPLES 48-61

Samples of polymers comprising resorcinol arylate polyester chainmembers were dried in vacuo at 120° C. for 15 hrs. A weighed sample ofabout 25-30 milligrams was placed in a circular die cavity 2 centimeters(cm.) in diameter and covered with a cylindrical piston of the samesize. The die assembly containing the sample was heated in a Carverpress at 290° C. for 5 minutes at 500-4,000 pounds gauge (lbs. g.)pressure, then removed and cooled in chill blocks. The heat treatmentproduced a film about 1 mil in thickness and 2 cm. in diameter.Molecular weights of samples before and after the heat treatment weremeasured by GPC using polystyrene standards. Table 4 shows examples ofmelt stability for resorcinol arylate polyesters prepared using themethod of Example 1 and Control Examples 1 and 2, and for resorcinolarylate-containing copolyestercarbonates prepared using the method ofExample 47. Wt. % resorcinol arylate in the Table refers to theapproximate wt. % resorcinol arylate chain members in the polymer, theremaining mers being organic carbonate mers.

TABLE 4 wt. % % Mw resorcinol % Mw Retention, Retention, Example arylatemelt test amine test^(f) 48^(a)  50 89.4 98   49^(a)  80 84   97.950^(a)  50 84.8 94   51^(b)  50 98.8 99.5 52^(b)  35 98.7 99.3 53^(a)100 55   62   54^(a) 100 55.9 61   55^(a) 100 45   40   56^(b) 100 87.586   57^(b) 100 97.7 99.6 58^(b) 100 99.5 99   59^(c) 100 12   25  60^(d) 100 46   74   61^(e) 100 77   78   ^(a)final reaction mixturestirred 5 min at pH 10 ^(b)final reaction mixture stirred 20 min at pH10-12 ^(c)Control Example 1 ^(d)Control Example 1 using 4 mole % phenolchain-stopper ^(e)Control Example 2 ^(f)following treatment withdiisobutylamine in solution

EXAMPLE 62

A resorcinol arylate polyester was prepared by the interfacial method ofControl Example 1 except that the organic solvent was dichloromethaneand a capping agent was present. Extrusion of the material gave orangepellets. The polymer had initial weight average molecular weight (Mw) of61,300 and Mw after extrusion of 52,200 (85% retention). A separatesample of material was treated with dibutylamine in solution; the Mw ofthe recovered material was 42,400 (69% retention).

EXAMPLE 63

A resorcinol arylate polyester was prepared by the method of Example 1.Extrusion of the material gave yellowish pellets. The polymer hadinitial Mw of 53,600 and Mw after extrusion of 50,800 (95% retention). Aseparate sample of material was treated with dibutylamine in solution;the Mw of the recovered material was 48,400 (90% retention).

EXAMPLE 64

A resorcinol arylate-containing block copolyester-carbonate with about50% by weight carbonate blocks and 1:1 ratio of isophthalate toterephthalate in the resorcinol arylate blocks was prepared by themethod of Example 47 except that the resorcinol arylate-containingpolyester block was made using the procedure of Control Example 1 usinga capping agent and dichloromethane as the organic solvent. Extrusion ofthe material gave amber pellets. The copolymer had initial Mw of 75,900and Mw after extrusion of 64,500 (85% retention). A separate sample ofmaterial was treated with dibutylamine in solution; the Mw of therecovered material was 73,000 (96% retention).

EXAMPLE 65

A resorcinol arylate-containing block copolyester-carbonate was preparedby the method of Example 47 with about 50% by weight carbonate blocksand 1:1 ratio of isophthalate to terephthalate in the resorcinol arylateblocks. Extrusion of the material gave faintly yellowish pellets. Thecopolymer had initial Mw of 52,300 and Mw after extrusion of 51,700 (99%retention). A separate sample of material was treated with dibutylaminein solution; the Mw of the recovered material was 51,500 (98%retention).

Disks were formed from the resorcinol arylate-containing polymers ofExamples 62-65. The disks were approximately 0.6 millimeters (mm) (0.024inches) thick and 50 mm (2.0 inches) diameter, and were formed frommelt-processed polymer (either pellets, extruded film, or injectionmolded parts) under the following conditions: 2.1 g of melt-processedpolymer were placed in a mold between heated platens of a hydraulicpress and heated at about 200° C. with no applied pressure for 3minutes, then under 4500 lbs. g. pressure for 1 minute, and finallyunder 6500 lbs. g. pressure for 1 minute. The mold was then rapidlycooled in ice water and opened to remove the disk.

The disks prepared as described were laminated onto injection-moldedplaques of LEXAN 140 polycarbonate (from General Electric Plastics)containing 2 wt. % of titanium dioxide pigment under the followingconditions to make well-adhered multilayer articles. All materials wereplaced in a heated (60° C.) vacuum desiccator overnight. A disk wasplaced onto an injection molded plaque of polycarbonate 2.5 inchessquare and one-eighth inch thick in a mold between heated platens of ahydraulic press and heated at about 200° C. with no applied pressure for2 minutes, then under 4500 lbs. gauge pressure for 1 minute, and finallyunder 6500 lbs. gauge pressure for 1 minute. All samples were welladhered.

The color of the disks and of the laminated plaques was determined on aGretagMacbeth™ Color-Eye 7000A colorimeter and reported as CIELAB valuesand yellowness index (YI; according to ASTM D1925). Results are shown onTable 5.

TABLE 5 Disks Laminate on PC (transmission) (reflection) Example L* a*b* YI L* a* b* YI 62 90.45 −1.23 15.2 26.01 76.6 3.57 31.74 61.07 6394.73 −0.3 3.61 6.34 86.18 −0.38 14.95 27.4 64 93.82 −0.43 5.4 9.5 84.210.88 20.44 38.27 65 95.52 −0.11 1.31 2.26 91.21 −0.8 6.95 12 unlaminated94.86 −0.52 2.88 4.51 PC

The data show that the disks and multilayer articles formed frommelt-processed resorcinol arylate-containing polymers made by a methodof the invention have much less color and lower yellowness index thanthe respective control blends.

EXAMPLES 66-74

In these Examples all the resorcinol arylate polymers comprisedstructural units derived from resorcinol and a 1:1 mixture of iso- andterephthaloyl dichlorides. The Examples used either a resorcinol arylatepolyester (Polymer A) or a resorcinol arylate block copolymer withbisphenol A polycarbonate (Polymer B with about 30 wt. % carbonateunits, or Polymer C with about 50 wt. % carbonate units). As stabilizeradditives, UV absorbers (“UVA”) available from Cytec Corp. wereemployed: CYASORB 5411 (UVA 1), CYASORB 531 (UVA 2), and CYASORB 1164(UVA 3). Films were cast from resorcinol arylate-comprising polymer bydissolving 2 grams of the polymer and any auxiliary UV absorber in 8milliliters of chloroform. The solution was drawn onto a glass plateusing 12 mil doctor blade and allowed to dry in air resulting in a filmabout 40 microns thick. The films were laminated onto injection-moldedplaques of LEXAN polycarbonate (from General Electric Plastics)containing 2 wt. % of titanium dioxide pigment under the followingconditions to make multilayer articles. Two layers of these films wereplaced on top of injection molded plaques comprising LEXAN, and theassembly was placed in a Carver press. The sample in the press washeated at about 210° C. with no applied pressure for 2 minutes, under4500 lbs. gauge pressure for 1 minute, and finally under 6500 lbs. gaugepressure for 1 minute. The films were well adhered to the substrates.The samples were exposed to weathering in an Atlas Ci4000 xenon arcweatherometer equipped with borosilicate inner and outer filters at anirradiance of 0.77 watts per square meter at 340 nanometers. Exposureconditions were black panel 63° C., dry bulb 43° C., humidity 30%,continuous illumination. The cycle was 102 minutes light followed by 18minutes with water spray. Samples were evaluated for color on aGretagMacbeth™ Color-Eye 7000A colorimeter with results reported as ΔE((ΔE=ΔL²+Δa²+Δb²)^(½)) and change in yellowness index (ΔYI; according toASTM D1925). Exposure was measured in kilojoules per square meter ofenergy recieved at 340 nanometers. Results are shown in Table 6. Theamount of UVA shown was based on total solids.

TABLE 6 UV Initial ΔYI at ΔYI at ΔE at Example Polymer Absorber YI 242kJ/m² 1127 kJ/m² 1127 kJ/m² 66 A none 5.49 11.02  12.76 10.37  67 A 1%UVA 1 6.06 8.74 10.57 8.66 68 B none 4.63 9.43 11.62 9.26 69 B 1% UVA 14.91 7.53  9.89 7.92 70 B 5% UVA 1 5.77 4.52  6.92 5.61 71 B 1% UVA 25.48 7.21  9.68 7.65 72 B 1% UVA 3 5.52 7.52  9.84 7.92 73 C none 4.738.66 11.80 9.18 74 C 1% UVA 1 5.08 7.31  9.96 7.87

In each case the use of 1% UVA reduced the amount of yellowing by about15%, while the use of 5% UVA reduced the amount of yellowing by about40%.

EXAMPLES 75-82

In these Examples the resorcinol arylate polymer comprised structuralunits derived from resorcinol and a 1:1 mixture of iso- andterephthaloyl dichlorides. The Examples used a resorcinol arylate blockcopolymer with bisphenol A polycarbonate containing about 15 wt. %carbonate units. As stabilizer additives, commercial stabilizers wereemployed, sometimes in combination with phosphorous acid. Phosphorousacid was employed as a 45 wt. % solution in deionized water. Stabilizeradditives were mixed with block copolymer before extrusion using asingle-screw extruder. The extruded mixture was molded into plaquesabout one-eighth inch thick. The color of the disks was determined andreported as yellowness index (YI; according to ASTM D1925). The resultsare shown in Table 7. The amounts of stabilizer used are reported inparts based on 100 parts resin (phr).

TABLE 7 Initial Example Stabilizer additive (phr) YI 75 none 17.2 76Bis(2,4-dicumylphenyl)pentaerythritol diphosphite 12.9 (0.03) 77Bis(2,4-dicumylphenyl)pentaerythritol diphosphite  9.2 (0.1) 78Bis(2,4-dicumylphenyl)pentaerythritol diphosphite  9.9 (0.1) + deionizedwater (0.1) 79 Bis(2,4-dicumylphenyl)pentaerythritol diphosphite  8.5(0.05) + phosphorous acid (0.005) 80Bis(2,4-dicumylphenyl)pentaerythritol diphosphite  7.1 (0.1) +phosphorous acid (0.005) 81 Bis(2,4-dicumylphenyl)pentaerythritoldiphosphite  7.0 (0.15) + phosphorous acid (0.005) 82Bis(2,4-dicumylphenyl)pentaerythritol diphosphite  6.9 (0.1) +phosphorous acid (0.01)

In each case the addition of phosphite stabilizer alone or incombination with phosphorous acid reduced the initial YI.

EXAMPLE 83

A resorcinol arylate block copolymer with bisphenol A polycarbonate asdescribed in Examples 75-82 was mixed with 0.0005 phr phosphorous acidand 0.1 phr bis(2,4-dicumylphenyl)pentaerythritol diphosphite using themethod described in Examples 75-82. Molded plaques showed YI of 8.3.

EXAMPLE 84

A resorcinol arylate block copolymer with bisphenol A polycarbonate asdescribed in Examples 75-82 was mixed with 0.005 phr phosphorous acidand 0.1 phr tris(2,4-di-tert-butylphenyl)phosphite using the methoddescribed in Examples 75-82. Molded plaques showed YI of 7.4.

EXAMPLE 85

A resorcinol arylate block copolymer with bisphenol A polycarbonate asdescribed in Examples 75-82 was mixed with 0.005 phr phosphorous acid,0.07 phr tris(2,4-di-tert-butylphenyl)phosphite, and 0.03 phr of ahindered phenol stabilizer using the method described in Examples 75-82.Molded plaques showed YI of 7.7.

EXAMPLE 86

In this Example the resorcinol arylate polymer comprised structuralunits derived from resorcinol and a 1:1 mixture of iso- andterephthaloyl dichlorides. The Example used a resorcinol arylate blockcopolymer with bisphenol A polycarbonate containing about 25 wt. %carbonate units. As stabilizer additive, phosphorous acid was employedas 10 wt. % solution in deionized water which was mixed with the blockcopolymer before extrusion using a twin-screw extruder. The extrudedmixture was molded into plaques 2.5 inches square and one-eighth inchthick. The color of the disks was determined on a GretagMacbeth™Color-Eye 7000A colorimeter and reported as yellowness index (YI;according to ASTM D1925). A plaque containing 0.2 wt. % phosphorous acidhad an initial YI of 11.1. For comparison a similar plaque made withoutphosphorous acid had an initial YI of 20.1.

EXAMPLES 87-100

In these Examples the resorcinol arylate polymer comprised a resorcinolarylate block copolymer with bisphenol A polycarbonate containing about10 wt. % carbonate units. The resorcinol arylate structural units werederived from resorcinol and a 1:1 mixture of iso- and terephthaloyldichlorides. As stabilizer additives, UV absorbers (“UVA”) wereemployed: CYASORB 5411 available from Cytec Corp. (UVA 1); CYASORBUV-3638 available from Cytec Corp. (UVA 4); and UVINUL 3030 availablefrom BASF Corp. (UVA 5). Table 8 shows physical properties for moldedparts of compositions containing various amounts of stabilizer additive.The value for “wt. % UVA detected” was determined by UV spectroscopy ona sample of copolymer recovered from a molded part. The value for “Mw inmolded part” was weight average molecular weight determined on a sampleof copolymer recovered from a molded part. Melt volume rate (MVR) wasdetermined using ASTM D1238. Notched Izod impact strength was determinedusing ASTM D256. Initial viscosity was determined at a frequency of 10radians per second using a Rheometrics Dynamic Spectrometer.

TABLE 8 % Mw MVR @ MVR @ Initial Viscosity Notched Notched wt. % wt. %Mw in change 300° C.; 300° C.; viscosity @ drop after Izod @ Izod @ UVAUVA molded relative to 6 min. dwell; 18 min. dwell; 300° C.; 30 min. @0° C.; 23° C.; Example added detected part powder cc/10 min. cc/10 min.poise 300° C. J/m J/m 87; UVA1 0 0   22344  −4.4 4.19 — 12499 +0.3 437805 88; UVA1   0.3 0.07 22530  −3.6 5.48 —  9555  −11 187 688 89; UVA1 10.45 19834 −15.2 8.54 —  6685  −35  21 197 90; UVA1 5 3.23 16959 −27.57.02 —  2131  −69  21  43 91; UVA4 0 0   24638    0   4.11 4.16 12124  +1 — 693 92; UVA4 1 0.93 24388  −0.9 4.60 4.62 11221 +0.3 — 480 93;UVA4 3 2.64 24487  −0.5 5.56 5.53  9432 +2.4 — 117 94; UVA4 5 4.33 24547 −0.3 6.44 6.45  8161 +4.5 —  53 95; UVA5 0 0   24005  −2.5 4.71 5.1112725 +2.1 — 757 96; UVA5   0.3 0.3  24005  −2.5 4.46 4.65 12922   +3 −650 97; UVA5 1 0.98 24101  −2.1 4.75 4.87 12067 −0.5 — 666 98; UVA5 32.88 24307  −1.3 5.23 5.61 10410 −6.3 — 469 99; UVA5 5 4.7  24398  −0.96.20 6.70  9213  −11 — 128 100; UVA5  8 7.15 24286  −1.4 7.37 8.63  7375 −24 —  69

The data in Table 8 show that both CYASORB UV-3638 and UVINUL 3030 aredetected in higher amounts in molded compositions than is CYASORB 5411.The data also show that compositions containing CYASORB UV-3638 orUVINUL 3030 had better retention of copolymer molecular weight in moldedparts than do compositions containing CYASORB 5411. Although theinvention is in no way dependent upon any theory of operation, it isbelieved that some UVA may be lost through volatilization during anextrusion compounding step and also through reaction with copolymer.

EXAMPLES 101-109

In these Examples the resorcinol arylate polymer comprised a resorcinolarylate block copolymer with bisphenol A polycarbonate containing about10 wt. % carbonate units. The resorcinol arylate structural units werederived from resorcinol and a 1:1 mixture of iso- and terephthaloyldichlorides: As stabilizer additives, UV absorbers (“UVA”) wereemployed: CYASORB 5411 available from Cytec Corp (UVA 1); CYASORBUV-3638 available from Cytec Corp. (UVA 4); and UVINUL 3030 availablefrom BASF Corp. (UVA 5). Table 9 shows physical properties for moldedparts of compositions containing various amounts of stabilizer additiveand either phosphorous acid or the bis-epoxide,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate. Values forphosphorous acid refer to parts per hundred parts resin (phr) of 45 wt.% aqueous phosphorous acid solution. The value for “Mw in molded part”was weight average molecular weight determined on a sample of copolymerrecovered from a molded part. Melt volume rate (MVR) was determinedusing ASTM D1238. The color of the disks was determined on 0.125 inchthick color chips at transmission mode and reported as yellowness index(YI; according to ASTM D1925).

TABLE 9 H₃PO₃ % Mw MVR @ MVR @ solution epoxide Mw in change 300° C.;300° C.; added, added, molded relative to 6 min. dwell; 18 min. dwell;Example phr phr part powder cc/10 min. cc/10 min. YI 101; UVA1 — — 21429−13    8.19 9.98 14.0 102; UVA1 0.005 — 23260 −5.5  5.88 6.79 11.0 103;UVA1 — 0.1 20464 −16.9  11.4  12.6  17.8 104; UVA4 — — 24388 −0.95 4.604.62 12.4 105; UVA4 0.005 — 23220 −5.69 5.24 5.54  8.73 106; UVA4 — 0.125073 +1.84 4.27 4.57 17.5 107; UVA5 — — 24101 −2.11 4.75 4.87 11.7 108;UVA5 0.005 — 23167 −5.91 5.76 5.76  8.50 109; UVA5 — 0.1 24421 −0.814.15 4.86 14.7

The data in Table 9 show that improved color was obtained using thecombination of phosphorous acid and UVA. The data also show thatimproved molecular weight retention was obtained using the combinationof epoxide and UVA, at least when the UVA is either of CYASORB UV-3638or UVINUL 3030.

EXAMPLES 110-111

FIG. 1 shows a graph of delta E vs. exposure in CIRA/sodalime xenon arclamp for a molded disk containing UVINUL 3030 and a resorcinol arylateblock copolymer with bisphenol A polycarbonate containing about 10 wt. %carbonate units.

The resorcinol arylate structural units were derived from resorcinol anda 1:1 mixture of iso- and terephthaloyl dichlorides. The disk comprisinga 10 mil layer of copolymer laminated onto a layer of white bisphenol Apolycarbonate. The data were collected under conditions similar to thoseof Examples 66-74 except using a CIRA inner filter and a sodalime outerfilter. The data show that the magnitude of delta E is decreased withincreasing amount of UVINUL 3030 in the coating layer.

FIG. 2 shows a graph of delta E vs. exposure in boro/boro xenon arc lampfor a molded disk containing CYASORB UV-3638 and a resorcinol arylateblock copolymer with bisphenol A polycarbonate containing about 20 wt. %carbonate units. The resorcinol arylate structural units were derivedfrom resorcinol and a 1:1 mixture of iso- and terephthaloyl dichlorides.The disk comprising a 10 mil layer of copolymer laminated onto a layerof white bisphenol A polycarbonate. The data were collected underconditions similar to those of Examples 66-74. The data show that themagnitude of delta E is decreased with increasing amount of CYASORBUV-3638 in the coating layer.

EXAMPLES 112-115

In these Examples the resorcinol arylate polymer comprised a resorcinolarylate block copolymer with bisphenol A polycarbonate containing about10 wt. % carbonate units. The resorcinol arylate structural units werederived from resorcinol and a 1:1 mixture of iso- and terephthaloyldichlorides. As stabilizer additives, there were employedbis(2,4-dicumylphenyl pentaerythritol) diphosphite (obtained asDOVERPHOS S9228 from Dover Chemical Corporation and referred to in Table10 as “diphosphite.”) and3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate; Table 10shows physical properties for molded parts of compositions containingvarious amounts of stabilizer additives following autoclaving at 105° C.Change in % haze (delta % haze) and change in YI values (delta YI) weredetermined according to ASTM D1925 on one-eighth inch thick moldedparts. Changes in weight average molecular weights were determined byGPC.

TABLE 10 Example 112 113 114 115 diphosphite, phr    0.03    0.03   0.03    0.03 epoxide, phr  0    0.03    0.06    0.10 delta YI 25 hrs. 0  0  0  0 50 hrs.  3  1  1  1 75 hrs.  9  2  2  2 90 hrs. 14  3  3  3140 hrs. 18  5  5  5 % Mw loss 25 hrs. 10  2  2  2 50 hrs. 24  3  3  375 hrs. 34  5  5  5 90 hrs. 47  9  9  9 140 hrs. 67 11 11 11 delta %haze 25 hrs.  2  2  2  2 50 hrs. 18  9  9  9 75 hrs. 39 13 13 13 90 hrs.64 19 19 19 140 hrs. 81 30 30 30

The data show that changes in YI, molecular weight, and % haze in moldedparts are decreased in the presence of diphosphite stabilizer and epoxyadditives.

EXAMPLES 116-123

In these Examples the resorcinol arylate polymer comprised a resorcinolarylate block copolymer with bisphenol A polycarbonate containingvarious wt. % levels of carbonate units. The resorcinol arylatestructural units were derived from resorcinol and a 1:1 mixture of iso-and terephthaloyl dichlorides. As stabilizer additives, UV absorberswere employed: CYASORB UV-3638 available from Cytec Corp.; and UVINUL3030 available from BASF Corp. Table 11 shows values for delta E vs.exposure in CIRA/sodalime xenon arc lamp for injection molded parts ofcompositions containing various amounts of stabilizer additives. Theparts were transparent plaques one-eighth inch thick. The data werecollected under conditions similar to those of Examples 66-74 exceptusing a CIRA inner filter and a sodalime outer filter.

TABLE 11 UVINUL UV- Delta E at wt. % 3030 3638 3284 6179 Example PC phrphr kJ/m² kJ/m² 116 70 — — 4.14 4.81 117 70 2 — 1.46 1.32 118 80 — —4.32 5.02 119 80 — 1 1.72 2.20 120 80 1 — 2.30 2.54 121 80 2 — 1.32 1.93122 90 — 3.72 4.03 123 90 2 1.51 1.49

The data show that changes in delta E in molded parts are decreased inthe presence of VINUL 3030 and CYASORB UV-3638.

While the invention has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present invention. As such,further modifications and equivalents of the invention herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the spirit and scope of the invention as defined by thefollowing claims. All U.S. Patents and patent applications cited hereinare incorporated herein by reference.

What is claimed is:
 1. A composition comprising (a) a thermally stable polymer comprising resorcinol arylate polyester chain members substantially free of anhydride linkages linking at least two mers of the polymer chain, and (b) at least one auxiliary stabilizer additive selected from the group consisting of 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.
 2. The composition of claim 1 further comprising at least one auxiliary stabilizer additive selected from the group consisting of a hindered phenol, an epoxide, a phosphite, and phosphorous acid, and mixtures thereof.
 3. A unitary or multilayer article comprising the composition of claim
 1. 4. A unitary or multilayer article comprising the composition of claim
 2. 5. The article of claim 3 which is a unitary article.
 6. A multilayer article comprising: a substrate layer comprising at least one thermoplastic polymer, thermoset polymer, cellulosic material, glass, or metal, and at least one coating layer thereon, said coating layer comprising the composition of claim
 1. 7. The article according to claim 6 wherein the substrate comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 8. The article according to claim 7 wherein the substrate comprises at least one polyolefin homopolymer, polyethylene, polypropylene, thermoplastic polyolefin, bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), or ABS or ASA copolymer.
 9. The article according to claim 6 wherein the coating layer further comprises at least one colorant.
 10. The article according to claim 6 wherein the substrate contains at least one of fillers and colorants.
 11. The article according to claim 6 further comprising at least one intermediate layer disposed between said coating and substrate layers.
 12. The article according to claim 11 wherein at least one intermediate layer is an adhesive layer.
 13. The article according to claim 11 wherein the intermediate layer contains at least one of fillers and colorants.
 14. The article according to claim 6 wherein said multilayer article is further applied to a substrate layer.
 15. The method according to claim 14 wherein the substrate layer comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 16. The article according to claim 3 which is an aircraft, automotive, truck, military vehicle, military aircraft, military water-borne vehicle, scooter, or motorcycle exterior or interior component, panel, quarter panel, rocker panel, trim, fender, door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill, mirror housing, pillar applique, cladding, body side molding, wheel cover, hubcap, door handle, spoiler, window frame, headlamp bezel, headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plate enclosure, roof rack, or running board; an enclosure, housing, panel, part, or trim for an outdoor vehicle or device, an electrical or telecommunication device, network interface device, outdoor furniture, aircraft, boat or marine equipment, outboard motor, depth finder, personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering, automatic teller machine (ATM), lawn or garden tractor, lawn mower, tool, lawn or garden tool, sporting equipment, toy, snowmobile, recreational vehicle, golf course marker, or playground equipment; an enclosure, housing, panel, part, or trim for a computer, desk-top computer, portable computer, lap-top computer, palm-held computer, monitor, printer, keyboard, FAX machine, copier, telephone, mobile phone, phone bezel, radio sender, radio receiver, meter, antenna, light fixture, lighting appliance, transformer, or air conditioner; an article used in building or construction, glazing, roofing, window, window trim, floor, wall panel, door, door trim, countertop, decorative window furnishing or treatment; a treated glass cover for a picture, painting, poster, or display item; a protected graphic; an outdoor or indoor sign; optical lens; ophthalmic lens; corrective ophthalmic lens; implantable ophthalmic lens; refractor; sheath for fluorescent tube; sleeve guard; an article made from a plastic-wood combination; a utility pit cover; shoe lace; cladding or seating for public transportation; cladding or seating for trains, subways, or buses; cladding for satellite dishes; coated helmet or personal protective equipment; coated synthetic or natural textiles; coated photographic film or photographic print; coated painted article; coated dyed article; coated fluorescent article; or coated foam article.
 17. A composition comprising (a) a thermally stable polymer consisting essentially of resorcinol arylate polyester chain members substantially free of anhydride linkages linking at least two mers of the polymer chain, and (b) at least one auxiliary stabilizer additive selected from the group consisting of 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.
 18. The composition of claim 17 further comprising at least one auxiliary stabilizer additive selected from the group consisting of a hindered phenol, an epoxide, a phosphite, and phosphorous acid, and mixtures thereof.
 19. A unitary or multilayer article comprising the composition of claim
 17. 20. A unitary or multilayer article comprising the composition of claim
 18. 21. The article of claim 19 which is a unitary article.
 22. A multilayer article comprising: a substrate layer comprising at least one thermoplastic polymer, thermoset polymer, cellulosic material, glass, or metal, and at least one coating layer thereon, said coating layer comprising the composition of claim
 17. 23. The article according to claim 22 wherein the substrate comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 24. The article according to claim 23 wherein the substrate comprises at least one polyolefin homopolymer, polyethylene, polypropylene, thermoplastic polyolefin, bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), or ABS or ASA copolymer.
 25. The article according to claim 22 wherein the coating layer further comprises at least one colorant.
 26. The article according to claim 22 wherein the substrate contains at least one of fillers and colorants.
 27. The article according to claim 22 further comprising at least one intermediate layer disposed between said coating and substrate layers.
 28. The article according to claim 27 wherein at least one intermediate layer is an adhesive layer.
 29. The article according to claim 27 wherein the intermediate layer contains at least one of fillers and colorants.
 30. The article according to claim 22 wherein said multilayer article is further applied to a substrate layer.
 31. The method according to claim 30 wherein the substrate layer comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 32. The article according to claim 19 which is an aircraft, automotive, truck, military vehicle, military aircraft, military water-borne vehicle, scooter, or motorcycle exterior or interior component, panel, quarter panel, rocker panel, trim, fender, door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill, mirror housing, pillar applique, cladding, body side molding, wheel cover, hubcap, door handle, spoiler, window frame, headlamp bezel, headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plate enclosure, roof rack, or running board; an enclosure, housing, panel, part, or trim for an outdoor vehicle or device, an electrical or telecommunication device, network interface device, outdoor furniture, aircraft, boat or marine equipment, outboard motor, depth finder, personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering, automatic teller machine (ATM), lawn or garden tractor, lawn mower, tool, lawn or garden tool, sporting equipment, toy, snowmobile, recreational vehicle, golf course marker, or playground equipment; an enclosure, housing, panel, part, or trim for a computer, desk-top computer, portable computer, lap-top computer, palm-held computer, monitor, printer, keyboard, FAX machine, copier, telephone, mobile phone, phone bezel, radio sender, radio receiver, meter, antenna, light fixture, lighting appliance, transformer, or air conditioner; an article used in building or construction, glazing, roofing, window, window trim, floor, wall panel, door, door trim, countertop, decorative window furnishing or treatment; a treated glass cover for a picture, painting, poster, or display item; a protected graphic; an outdoor or indoor sign; optical lens; ophthalmic lens; corrective ophthalmic lens; implantable ophthalmic lens; refractor; sheath for fluorescent tube; sleeve guard; an article made from a plastic-wood combination; a utility pit cover; shoe lace; cladding or seating for public transportation; cladding or seating for trains, subways, or buses; cladding for satellite dishes; coated helmet or personal protective equipment; coated synthetic or natural textiles; coated photographic film or photographic print; coated painted article; coated dyed article; coated fluorescent article; or coated foam article.
 33. A composition comprising (a) a thermally stable copolymer comprising resorcinol arylate polyester chain members in combination with C₃₋₂₀ straight chain alkylene, C₃₋₁₀ branched alkylene, or C₄₋₁₀ cyclo- or bicyclo-alkylene chain members, substantially free of anhydride linkages linking at least two mers of the polymer chain, and (b) at least one auxiliary stabilizer additive selected from the group consisting of 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.
 34. The composition of claim 33 further comprising at least one auxiliary stabilizer additive selected from the group consisting of a hindered phenol, an epoxide, a phosphite, and phosphorous acid, and mixtures thereof.
 35. A unitary or multilayer article comprising the composition of claim
 33. 36. A unitary or multilayer article comprising the composition of claim
 34. 37. The article of claim 35 which is a unitary article.
 38. A multilayer article comprising: a substrate layer comprising at least one thermoplastic polymer, thermoset polymer, cellulosic material, glass, or metal, and at least one coating layer thereon, said coating layer comprising the composition of claim
 33. 39. The article according to claim 38 wherein the substrate comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 40. The article according to claim 39 wherein the substrate comprises at least one polyolefin homopolymer, polyethylene, polypropylene, thermoplastic polyolefin, bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), or ABS or ASA copolymer.
 41. The article according to claim 38 wherein the coating layer further comprises at least one colorant.
 42. The article according to claim 38 wherein the substrate contains at least one of fillers and colorants.
 43. The article according to claim 38 further comprising at least one intermediate layer disposed between said coating and substrate layers.
 44. The article according to claim 43 wherein at least one intermediate layer is an adhesive layer.
 45. The article according to claim 43 wherein the intermediate layer contains at least one of fillers and colorants.
 46. The article according to claim 38 wherein said multilayer article is further applied to a substrate layer.
 47. The method according to claim 46 wherein the substrate layer comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 48. The article according to claim 35 which is an aircraft, automotive, truck, military vehicle, military aircraft, military water-borne vehicle, scooter, or motorcycle exterior or interior component, panel, quarter panel, rocker panel, trim, fender, door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill, mirror housing, pillar applique, cladding, body side molding, wheel cover, hubcap, door handle, spoiler, window frame, headlamp bezel, headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plate enclosure, roof rack, or running board; an enclosure, housing, panel, part, or trim for an outdoor vehicle or device, an electrical or telecommunication device, network interface device, outdoor furniture, aircraft, boat or marine equipment, outboard motor, depth finder, personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering, automatic teller machine (ATM), lawn or garden tractor, lawn mower, tool, lawn or garden tool, sporting equipment, toy, snowmobile, recreational vehicle, golf course marker, or playground equipment; an enclosure, housing, panel, part, or trim for a computer, desk-top computer, portable computer, lap-top computer, palm-held computer, monitor, printer, keyboard, FAX machine, copier, telephone, mobile phone, phone bezel, radio sender, radio receiver, meter, antenna, light fixture, lighting appliance, transformer, or air conditioner; an article used in building or construction, glazing, roofing, window, window trim, floor, wall panel, door, door trim, countertop, decorative window furnishing or treatment; a treated glass cover for a picture, painting, poster, or display item; a protected graphic; an outdoor or indoor sign; optical lens; ophthalmic lens; corrective ophthalmic lens; implantable ophthalmic lens; refractor; sheath for fluorescent tube; sleeve guard; an article made from a plastic-wood combination; a utility pit cover; shoe lace; cladding or seating for public transportation; cladding or seating for trains, subways, or buses; cladding for satellite dishes; coated helmet or personal protective equipment; coated synthetic or natural textiles; coated photographic film or photographic print; coated painted article; coated dyed article; coated fluorescent article; or coated foam article.
 49. A composition comprising (a) a thermally stable block copolymer comprising resorcinol arylate polyester segments in combination with organic carbonate segments, substantially free of anhydride linkages linking at least two mers of the polymer chain, and (b) at least one auxiliary stabilizer additive selected from the group consisting of 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) and 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane.
 50. The composition of claim 49 further comprising at least one auxiliary stabilizer additive selected from the group consisting of a hindered phenol, an epoxide, a phosphite, and phosphorous acid, and mixtures thereof.
 51. A unitary or multilayer article comprising the composition of claim
 49. 52. A unitary or multilayer article comprising the composition of claim
 50. 53. The article of claim 51 which is a unitary article.
 54. A multilayer article comprising: a substrate layer comprising at least one thermoplastic polymer, thermoset polymer, cellulosic material, glass, or metal, and at least one coating layer thereon, said coating layer comprising the composition of claim
 49. 55. The article according to claim 54 wherein the substrate comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 56. The article according to claim 55 wherein the substrate comprises at least one polyolefin homopolymer, polyethylene, polypropylene, thermoplastic polyolefin, bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), or ABS or ASA copolymer.
 57. The article according to claim 54 wherein the coating layer further comprises at least one colorant.
 58. The article according to claim 54 wherein the substrate contains at least one of fillers and colorants.
 59. The article according to claim 54 further comprising at least one intermediate layer disposed between said coating and substrate layers.
 60. The article according to claim 59 wherein at least one intermediate layer is an adhesive layer.
 61. The article according to claim 59 wherein the intermediate layer contains at least one of fillers and colorants.
 62. The article according to claim 54 wherein said multilayer article is further applied to a substrate layer.
 63. The method according to claim 62 wherein the substrate layer comprises at least one homo- or copolymeric aliphatic olefin or functionalized olefin polymer, polycarbonate, polyester or addition polymer of an alkenylaromatic compound.
 64. The article according to claim 51 which is an aircraft, automotive, truck, military vehicle, military aircraft, military water-borne vehicle, scooter, or motorcycle exterior or interior component, panel, quarter panel, rocker panel, trim, fender, door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill, mirror housing, pillar applique, cladding, body side molding, wheel cover, hubcap, door handle, spoiler, window frame, headlamp bezel, headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plate enclosure, roof rack, or running board; an enclosure, housing, panel, part, or trim for an outdoor vehicle or device, an electrical or telecommunication device, network interface device, outdoor furniture, aircraft, boat or marine equipment, outboard motor, depth finder, personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering, automatic teller machine (ATM), lawn or garden tractor, lawn mower, tool, lawn or garden tool, sporting equipment, toy, snowmobile, recreational vehicle, golf course marker, or playground equipment; an enclosure, housing, panel, part, or trim for a computer, desk-top computer, portable computer, lap-top computer, palm-held computer, monitor, printer, keyboard, FAX machine, copier, telephone, mobile phone, phone bezel, radio sender, radio receiver, meter, antenna, light fixture, lighting appliance, transformer, or air conditioner; an article used in building or construction, glazing, roofing, window, window trim, floor, wall panel, door, door trim, countertop, decorative window furnishing or treatment; a treated glass cover for a picture, painting, poster, or display item; a protected graphic; an outdoor or indoor sign; optical lens; ophthalmic lens; corrective ophthalmic lens; implantable ophthalmic lens; refractor; sheath for fluorescent tube; sleeve guard; an article made from a plastic-wood combination; a utility pit cover; shoe lace; cladding or seating for public transportation; cladding or seating for trains, subways, or buses; cladding for satellite dishes; coated helmet or personal protective equipment; coated synthetic or natural textiles; coated photographic film or photographic print; coated painted article; coated dyed article; coated fluorescent article; or coated foam article. 